Base-Metal Catalysis

Welcome to the latest webcheminar in our series presented by Tima. I am Toby Reeve, editor of Science of Synthesis. Today's topic is Base Metal Catalysis, and we have four speakers sharing their recent work. Professor Naohiko Yoshikai will be chairing the session. Thank you for joining us.

I will be handing over to him in a few moments before we begin. There are a few general comments about today's event that I'd like to make. The seminar is being recorded and the recording may be shared later on various platforms such as YouTube. You will receive a link to this recording by email shortly after the event.

As the audience, you will be kept on mute throughout the session, but we do encourage you to submit questions for the speakers. Please type these into the Q and A window on the GoTo platform, which hopefully you can see. As many of these as possible will then be answered after each of the talks.

If you wish, you can include your name and affiliation with your question. We will try to mention these details when the questions are asked. Keep an eye on the chat panel window for information about the speakers and links to their published content, including some Reviews from Science of Synthesis that are currently free to read to celebrate this event.

A quick word about our portfolio of publications and products: at Team of Chemistry, we specialize in publications and products related to synthetic methods and organic chemistry. You may be familiar with our journals, Synthesis and Synlett, as well as our fully open access journals, SynOpen and Organic Materials. Keep these journals in mind when considering where to submit your research.

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We will be open for submissions for this journal very soon. Today's webinar topic was chosen to celebrate the recent publication of two volumes of Reviews on Topics in Base Metal Catalysis. The series was edited by Professor Naohiko Yoshikai, our Chair for today's webinar. The editorial office would like to express immense gratitude to Naohiko for his dedication and thorough approach in editing this series.

Volume one, focusing on copper and nickel catalysis, was published at the end of last year. Volume two, which covers cobalt, iron, manganese, and chromium catalysis, was completed this month. Many reviews from volume two are already available online on ESOS as Early View content. In total, this series includes 34 reviews. We would like to thank all the authors who contributed to this series.

Three authors from the volume two reviews will be speaking in today's webinar. Later in the session, I will demonstrate how to access the content of the Base Metal Catalysis volumes online using the current platform of ESOS.

To start off, I would like to introduce our chair for today, Professor Yoshikai. Born in 1978 and raised in Tokyo, Professor Yoshikai received his BS, MS, and PhD degrees from the University of Tokyo under the guidance of Professor I Aichi Nakamura. He served as an assistant professor at the same institute before moving to Singapore in 2009 to join the faculty at Nanyang Technological University. In 2016, he was promoted to Associate Professor with tenure. In 2021, he returned to Japan as a full Professor at Tohoku University. Professor Yoshikai's research focuses on exploring new reaction chemistry using transition metal catalysts and main group reagents for selective organic synthesis. I will now hand over to Professor Yoshikai to introduce the first speakers. Thank you for joining us today.

Thank you Toby for the kind introduction and for arranging this event. I am NAAI from the university. It is a great pleasure to share this with you. The webinar on Base Metal Catalysis features four speakers from Asian countries: two from China, one from Singapore, and one from Japan. This webinar was organized to promote the recently completed two volumes of science Subsys Reference Library, Base Metal Polys.

Let me take a few minutes to introduce the background and contents of this reference library. In 2020, I was invited to edit an SOS volume focused on Base Metal Polys. The definition of Base metal can vary depending on the context, but for this volume, we focused on the earth's abundant transition metals or 3D metals ranging from copper in group 11 to chromium in group six of the periodic table of elements to achieve coherence in the context.

The project took a long time due to COVID-19 and my personal relocation, but I am pleased to see it finally taking shape. I would like to thank the HDR Office, specifically Toby, Alex, and Karen, as well as the authors, including today's speakers, Professor Min Ko, Zang Lu, and Taiko Yoshino, for their contributions. I want to express my sincere thanks for their outstanding support.

Volume one, which is available online, focuses on copper and nickel catalysis, covering topics such as cross-coupling, CH activation, functional group installation, trifluoromethylation, carboxylation, oxidation, and functional group shuttle chemistry. Volume two concentrates on cobalt, iron, manganese, and chromium catalysis, along with cross-coupling and CH activation, which are also discussed in volume one.

This volume covers various types of transformations, such as Hydrosilylation, hydroboration, Luis acid or Catalysis, ch oxidation hydrogenation, metal hydride hydrogen atom transfer, MH A T type Transformation, and nozaki Yakish type reactions.

Base Metal Catalysis is unique due to its distinct attributes. This slide summarizes some of the characteristics that make Base Metal Catalysis stand out.

Base metals have unique properties compared to their heavier congeners, such as smaller orbital energy splitting, weaker metal ligand bonding, lower electronegativity, smaller coherent body, and lower reduction potentials. These properties can lead to unique reactivities, such as one-electron redox bond homolysis, high opacity of high-valence species, and strong globality of low-valence species. This reactivity can often lead to mechanistic complications, but also allows for the exploitation of unique mechanistic concepts for catalysis, such as electron transfer, radical relay, redox-active ligands and substrates, oxidative-induced reductive ation, and ligand hydrogen transfer.

Furthermore, these unique properties provide an excellent opportunity for merging with photo and electrochemistry. Readers are encouraged to explore recent volumes on photocatalysis and catalysis. These remarks serve as an introduction to the following invited lectures. The first speaker is Lin Lin Chu from Donghua University. Professor Chu obtained her bachelor's degree in 2007 from Harvard University of Technology and began her PhD studies the same year with Professor F. Lin Qing at SIOC. Her research focused on a new method for isolating a ka mid-oxidated tr.

In 2013, she joined Professor David McMillan's laboratory at Princeton as a postdoc to work on photoredox catalysis. In 2016, she started her independent career at Dona University, focusing on transmittal catalysis and radical chemistry. She is a member of the Early Career Advisory Board of Science of Sciences.

Today's lecture, titled "Ame Radical Multicomponent Cross Coupling Sphere N Catalysis," will be presented by Professor Z. Thank you to Professor Ishika for the introduction and to Professor Ya for the invitation. It is a great pleasure to participate in this webinar and share our recent research progress in ego catalyze the radical market component across couplings.

Radicals, also known as free radicals, are molecules with at least one unpaired electron. They are short-lived, highly active, and exhibit certain similarities to classic carbonyl intermediates. Radicals are versatile and useful synthetic intermediates in many important chemical transformations, including natural products and polymerization.

The rapid development in the field of photos and electrochemical synthesis has led to advancements in radical chemistry. However, the high reactivity of radicals poses challenges to controlling their selectivity. Radicals have low barriers for reaction and can easily form undesired species through rapid diffusion. This makes controlling the selectivity of radicals difficult.

Chemists have made significant progress in understanding radical mechanisms and have developed catalytic methods using carboxylic acids or organic catalysts to control radical additions. This has led to efficient and powerful platforms for developing new and efficient radical couplings with high selectivity.

Despite these achievements, developing catalytic methods for asymmetrical radical couplings remains a challenge. N-catalysis is particularly interesting due to its low cost, abundance, versatility, and selectivity in radical couplings. This presents a promising avenue for eco-friendly catalysis.

The generally proposed reaction pathway for metal-catalyzed couplings involves a key step where an LP radical is captured by a car and a N two complex to form the next three species. The N three species is then expected to undergo Reduction elimination to deliver the C Products. However, the process is complicated by the fact that the N three species is prone to undergoing a reversible nick carbon bond homolysis to regenerate the LG radical anemic two species. This reversible process makes the expected stereoselective radical capture process inefficient. As a result, the entire transformation of these radical couplings relies on the final Reduction to delivery.

The invention of reversible homely processes in products has inspired chemists like Greg Friman to develop elegant initial convergence across couplings. Electrophile couplings are impressive. However, the reversible feature also presents challenges in developing more efficient and asymmetric radical coupling modes. These modes aim to provide easier and higher precision control for efficient radical symmetrical couplings.

Over the last several years, we have developed two strategies to address this challenge: the Chelation strategy and the Sensitization strategy. The Chelation strategy aims to provide alternative or more complicated sterlings in the relation strategy by establishing a direct relation between the pendent functional group and the NCO, which facilitates the LG radical to selectively add to the N center to form a three species. Chelation also benefits from forming a more rigid NCO complex with a favorite Reda elimination that may impede the reverse for eco carbon in the Sensitization strategy.

In the Sensitization strategy, the photoexcitation of the planar ground state need to complex with light will bring the NN two species from its planar to its exact state.

The change in the gene of the Nickel complex could allow for a selective radical capture process. Four excitations would enhance activity and selectivity through single electron or energy transfers. Selective control is important in photo-excited states.

In 2016, our group was interested in multi-component cross couplings because they can efficiently build complex molecules using simple materials. We anticipated that radical species would bring distinct activities and selectivity to these reactions. However, progress in this area has been slow due to the presence of multiple types of radical species, making it challenging to use a single Transition Metal catalyst to control the selectivity.

We focused on a Multicomponent radical component system to test our proposed Chelation and Sensitization strategies for reactivities. Several examples developed over the last few years will be shown to demonstrate our Reaction design.

The first example is a symmetric three component radical coupling of nonactivated L kins. The Reaction design involves adding LT radical to the L kins to form a second rate and not stabilize the L key radicals. With the relation between the functional group and Nickel, the L radical selectively captures the P KCOM to form a three and then undergoes reductive amination to deliver the three component symmetrical coupling Products.

To achieve the ster electric, the radical capture step is crucial for the success of three-component coupling reactions. After some initial attempts, we selected the endo carbon carbonic acid derived LK ers as the template substrate, the pro LKLD as the radical producers, and a bromide as the carbon partners.

After some initial exploration, we found that substituting oxalin with Linton, also known as au ligand, allowed for successful three-component coupling with 97 carbon or 99 carbon LT subsid. Additionally, using car ligand in August resulted in high yield and initial selectivity control for the three-component coupling.

We also investigated the use of commonly used steroid-demanding car ligands like pie box and box, which did not produce any product. This suggests that different reaction pathways may be involved in these reactions.

Optimizing the reaction conditions for three-component radical couplings showed a wide substrate scope, excellent functional groups, and a variety of areas for each of the three components. Under these optimal conditions, the NOFI cross cos delivered final products with high yield and ease.

With the carbonic ester on hand, we can synthesize a number of other benzomotives easily.

This type of composite is not readily available through other known methods. This strategy can be applied to radical couplings between nonactivated LK iodide and bromides to produce high-quality products, demonstrating the effectiveness of these chelation strategies.

To investigate the role of the group in our strategies, we conducted control reactions. By using LP S to enrich the electron density, we aimed to make the electron more nucleophilic. This led to higher selectivity control with carbonic acid. However, increasing the ring size of the cyclic structures from six to seven or removing the substituent group resulted in a significant decrease in activity control.

The conformity result is an important tradition effect in this system. Below is the proposed reaction pathway for the three-component asymmetrical coupling interactions of L keys.

I will not go into detail due to time constraints. The key step involves the LG radical between the functional group and the N. The LT radical is expected to undergo selective radical capture to form the N three species, followed by reductive amination to produce the final product.

By using a specific strategy, we were able to achieve the first example of the carbon alkylation of β-γ unsaturated ketones. This was done by using LK highlights as coupling partners in the presence of Nickel cod and substituting with Ox Liki. This chemistry also demonstrates a good substrate scope and excellent initial selectivity control. The addition of benzoic acid was found to be important in enhancing efficiency. It is speculated that the nuclear cycles intermediate may be crucial in achieving high initial selectivity control for carbon alkylation.

Our second strategy involves a sensitization method using visible light to excite the planar ground state complex to its excited state.

The expected aster selective radical capture step is not fully explored due to changes in geometry. The ground state planar integral with a bent ligand can transition to a tetrahedron excited state through excitation. In photocatalysis, the absence of XX allows the N 23 to exist in a long-lived tetrahedral state, exhibiting diverse activities in photo reductase transformations.

We expected that the radical capture by the excited tetrahedron iron complex could be selective. This enabled the three-component radical couplings between the kins area allies and LK travel borrow, using synthetic photo reduction and legal analysis to deliver the coupling products. With this simple thought in mind, we began to explore the possibility of this reaction design. Recently, we found that using the simple iridium-based catalyst and the carboxylate, along with a catalyst combination under blue air irritation, allowed for the development of three-component couplings between the L LP Traveler Boris and a bromide to deliver the expected α coupling related cari and excellent ease.

The three-component reaction demonstrates excellent substrate scope and initial selectivity control. The compounds produced are important skeletons found in many biologically active compounds. The reaction is sensitive to basic conditions due to the car centers.

These photoredox catalysts offer a more benign protocol for accessing valuable structures under mild conditions. The Multicomponent reaction mode allows for modulation and easy access to a library of variables. For example, changing the structure of LQ traveler bo and using L kins and braide can easily produce derivatives of the fibro with high efficiency and excellent initial selectivity control.

This chemistry can be used to quickly synthesize lead compounds for programs using simple study materials. The process only takes three steps, which is shorter than previous reports. Mechanism studies were conducted to probe the reaction pathway. The first study involved a radical probe reaction with sac protein Alkins and Temples, indicating the involvement of α carbon radicals.

We collaborated with Professor Ozma Gui, now at Texas A&M University, to better understand the chemo- and stereo-selectivity in these three-component modes. We found that the radical addition rate to the excited LK complex is much faster than to the excited triplet AIC2 complex. This is excellent for security. Additionally, we discovered that the radical capture by the tetrahedron excited AIC2 complex is the stereodetermining step for this asymmetric direction. Analysis also revealed that non-covalent interactions between the areas or the car ligand are important for achieving higher selectivity control. Similar to previous reports, we found that the N3 species generated from the ground state N2 is prone to radical recombination for N-C bond homolysis, posing challenges for achieving higher selectivity control.

Our proposed pathway for synergistic reduction and chemistry involves a photoexcited catalyst that undergoes a single electron transfer with a tertiary group, releasing radicals that are added to a ketone to form an alpha radical. For the nitrogen cycle, we start with N zero and add it to a bromide to form a ground state species, which then reacts to form an alpha radical, N three, and undergoes reduction and elimination to produce the final product. Single electron events between reducing first catalysts close the two catalytic cycles.

Photocatalysis can engage in single electron transfer and energy transfer with organometallic species, leading to exciting possibilities. Energy transfer can be used to track specific regions, allowing for the production of both cis and trans products. For example, in a three-component reaction involving an alkene, selective enrichment of both cis and trans products can be achieved using two specific photocatalysts.

For the initial selectivity control of the α phosphines phosphine carbon center, we found that using the car by emit ligand with the electron deficient ar ar R substitute is optimal for controlling the SP three carbon centers. Mechanism studies and star war quant studies indicated that the photoexcitation of each is matched, suggesting energy transfer between the photoexac catalyst and the LK bromide. Control reactions with both trans and clk bromide were also conducted. Calculations of triple energy supported our assumption that in this system, PC one with slightly higher trip energy can engage electron transfer.

Energy transfer occurs with the trans LK Products, which are then delivered to the CCLK Products. PC two, with lower energy transfer, can only afford transversion for the synthesis of the valuable L kin OIC phosphonate. FD calculation showed that the interaction between phosphines and L kin directs the LK radical selectivity to add the triplet, the L kin traveler, L kin nickels. This step is the stereodetermining step in carbon alkyne formations.

With the optimal man, we can easily use tools to simplify photo copies. This allows us to achieve the Z ester divergence and the initial selective carbon calculations of one phosphate. By delivering these already phosphate with a high standard selectivity and initial selectivity control.

We can use paralytic phosphines in chemistry to synthesize a variety of biologically active LK or L kin phosphines. These phosphines can be easily manipulated with high ease.

The Sensitization strategy enables us to develop symmetrical carbon-carbon functional relations of L kins. This strategy can also be used to tune the reactivity and selectivity of L kin radical by generating.

The radical addition to the readily available L kinds has led to the development of several systems for the functionalization of L kins. This includes terminal and internal L KS to efficiently construct substitute L Kins with high efficiency.

I would like to thank my students for their hard work, collaborators for their excellent contributions, and founders for the financial support. Thank you for listening. I am happy to take any questions. Thank you for a excellent talk. Now, we are in the Q and A session. I will accept questions from the audience or panelists. It seems there are no questions at this moment, so let me start. It appears that the biox type ligand is very effective in your reaction compared to the conventional box type ligand. Can you comment on the electronic or steric nature of this ligand and why it is more successful in promoting the reaction? Thank you for your question. Based on my understanding, the biox ligand is non-redox active, making it effective in participating in radical couplings in my chemistry. This could be the main reason for its success in the reaction. Do you mean that the ordinary box type ligand has redox active properties? Yes, that is correct. The redox activity of the ligand plays a role in the reaction design, where the radical is selectively captured by the biox ligand to form a complex. This allows for efficient reductive elimination to deliver the final product. Thank you for clarifying. Any questions from the panelists? Can you show page 35? Oh, yes, here it is. On the top scheme, you show that the ground state Nickel two complex can capture the radical reversibly, leading to the formation of a Nickel three species. What is the difference in radical capture between the species on the left and right side of the scheme? Under photoirradiation, the ligated Nickel two complex undergoes a change in geometry to a tetrahedral state, which facilitates efficient reductive elimination when the radical is added. This is different from adding the radical to a planar Nickel two complex, which may result in reversible reactions. Our calculations support this hypothesis, showing that the tetrahedral Nickel three species is more effective in delivering the final product. Thank you for the explanation. Is there a difference in radical capture between internal and terminal alkynes in your reaction? The synthetic challenge with internal alkynes is greater than with terminal alkynes, but it also offers more diversity in directing groups. We have successfully achieved the di-functionalization of internal alkynes under our conditions. Thank you for sharing. Any other questions? In the stereodetermining step on your slide, is the R step related to reductive elimination? No, the R step is not reductive elimination. The generation of the tBu radical is not likely in this specific reaction. The energetic challenge lies in the N-metallated cross coupling step. Thank you for clarifying. Due to time limitations, I will need to close this session. Thank you for a great talk. Thank you. Let's move on to the second speaker, Dr. Mingo from the National University of Singapore. He completed his bachelor's at NTU in 2012 and his PhD and postdoc at Boston College with Professor Amir Obe from 2012 to 2018.

He joined the Department of Chemistry at NUS as the first President's Assistant Professor. He is considered a rising star in the field and has received numerous recognitions, including being one of the 12 most talented individuals in the class of 2022 and receiving the Young Scientist Award from the Singapore National Academy of Science. He recently secured his tenure. Today, he will be discussing anesthetic cyclic a car and catalysis. Thank you, Professor Yoshikai, for the introduction. I previously worked with Amir Hove before returning to Singapore. I am now an Associate Professor at the National University of Singapore.

Before I begin today's talk, I want to discuss our research motivation. One of the motivations in my group is to address challenges facing the chemical industry. One of these challenges is the overreliance on precious metals. Professor Yoshikai has emphasized the importance of base metals. Base metals are more abundant and less expensive compared to precious metals, as shown in the product table.

Base metal catalysts have the potential to simplify organic synthesis. In chemical synthesis, the more materials used, the more waste, energy consumption, and manpower needed. This can lead to downstream issues such as increased CO2 production, which contributes to environmental problems like global warming.

Our strategy to address these issues is to use base metal chemistry to develop new processes. A recent review in Advanced Materials describes the carbon footprints of various transition metals in terms of global warming potential.

Base metals have lower global warming potential compared to precious metals, making them a more environmentally friendly option. Additionally, using Base Metal Catalysis provides added incentives for their use. Base metals have unique properties that allow for distinct reactivity and selectivity profiles, creating new opportunities for faster and more cost-effective molecule production. In the past five years, a series of base metals have been developed to promote organic sciences and simplify the preparation of organic compounds, ultimately reducing carbon footprints in accessing these molecules.

In my group, we work on harnessing base metal catalysts and radical chemistry to develop new chemical processes across chemical science. This includes functionalization to create small molecule building blocks, stereoselective carbohydro synthesis for medicinal applications, and developing heterogeneous catalysts with material chemists for liquid phase organic synthesis. Recently, we have started a program where we collaborate with polymer chemists to upcycle waste plastics using base metal catalysts to activate polymer compounds and create new functional polymers for various applications.

Is alkene functionalization a good follow-up to Professor Chu's presentation? She explained why these reactions are important. Alkenes serve as regions where different components can be merged to create complex structures. This allows for rapid assembly of molecules and creates diversity in a quick manner.

The saturated products obtained at the end can be used as building blocks to create important compounds. It is similar to assembling Lego blocks on a molecular scale to create complex structures in one process, which is very appealing.

One of the challenges we faced when we first entered this field a few years ago was using Base Metal Catalysis to promote Darle Functionalization. This involves adding carbon-based functional groups across unactivated Alkanes, which are particularly difficult substrates for this type of reaction.

For example, when using activated Alkanes like styrenes, the carbonation process is very efficient and typically results in a single visual isomer due to the high site selectivity. However, when using unactivated Alkanes, the carbonation process is slower and results in a mixture of two visual isomers due to the weak electronic and steric bias of the added functional group.

To address this challenge and achieve high efficiency and high site selectivity with unactivated Alkanes, a solution needs to be developed.

Over the years, several strategies have been introduced. One such strategy involves substrate control using intra molecularity. In this method, the key tethered to the electrophile undergoes an intramolecular carbonation. By functionalizing the carbon and forming a second CC bond, a single visual of the product can be obtained. However, this approach is limited to certain specific compounds.

The second strategy involves using directing groups as auxiliaries. In this method, an alkene is tethered to a directing auxiliary that guides the carbonation process. It is important to carefully control the distance between the directing group and the metal to avoid poor selectivity and inefficient carbonation.

The groups of jury angle have developed directing groups over the years to facilitate the process.

The third strategy popularized by various groups, including the Neva and Professor Chu theories, involves using radicals. By using activated light in the presence of a metal radical, site selectivity can be added to the alkene. This allows for functionalization of a carbon metal and the production of a product with good activity. However, there is a restriction on the types of groups that can be formed or installed, as only certain groups that can generate stabilized radicals are allowed.

To address this limitation, we aimed to develop a complementary strategy to the existing reactions using a car.

We wanted the writing group to be free using an electron-donating ligand to enhance visual activity. There are 22 differentiating complexes summarized in a review by Steve Nolan - Nickel carbon complexes and metal energy complexes. These complexes are known to be bulky for stabilization. Upon closer inspection, the Nickel carbon bond is less than two angstroms, slightly shorter than a Nickel phosphine bond.

Hins may exert a slightly larger static pressure around the metal center compared to phosphines. Are there any precedents for using carbon or phosphate metal complexes to induce high visual selectivity? For example, in 2012, Professor Naked studied a visual selective hydro elevation reaction where the transition state favored avoiding static repulsion between the ligand on the Nickel and the alkane substitute.

To avoid standard diffusion and favor using visual cues for organometallic species, which will translate to high selectivity in the final product. In a second example from Tim Jamieson's group, a bulky phosphine ligand was introduced to promote highly branched selective Heck reactions.

The favorite transition state is one that avoids repulsion between the bulky phosphate and the alkane substitute. This would generate a single visual isomer of the species that will undergo β hydro elimination to give the branch of Ky. We wanted to see if we could access this same intermediate by functionalizing the carbon Nickel bond with a carbon carbon bond to get die carbon organization without using a directing auxiliary. Through extensive optimization, we found that carbon energy car NTC carin nickel complexes are good catalysts to promote such reactions. By using electrophile and organometallic regions such as magnesium or zinc regions, you can promote directing group free dye ation with good activity. This method works across different types of ores without going through radical intermediates.

The mechanism involves octave addition followed by visual selective cation to avoid repulsion between the ligand and the substituent. To form the intermediate for further reductive elimination, perform a trans trans. This will bring you back to the starting complex and generate the desired product with good reactivity.

We can functionalize Alkins, including 11 does, to generate sterically congested quaternary centers. These centers are difficult to make but can provide good regioselectivity. Our Alkins do not contain any directing groups or weakly directing groups.

Activated alkanes such as styrenes, danes, and nitrogen-substituted alkanes can undergo functionalization with good reactivity. By adjusting the functionality on the electrophile or the nitrogen fragment, various derivatives can be obtained with high site selectivity and tolerance for different functional groups.

We can utilize elevation for error functionalization by changing the identity of the organic metallic region to incorporate LQ groups or groups and alkalic groups. This process is used to simplify organic synthesis and create intermediate five, which can be further elaborated into compounds in fewer steps compared to previous synthetic routes.

By using a catalyst to control visual selective carbonation, we can generate intermediate age selectively. This allows us to function as the carbon Nickel bomb with organometallic region to form compound seven. Switching to a coy, which can give you a hydride donor, allows you to introduce a hydrate and get hydrocarbon functionalization products selectively.

We expanded the scope of Hydrofunctionalization by using various types of Alkanes, including unactivated Alkanes and Hector at sub Alkanes. These Hydrofunctionalization Products only work for cyclic Alkanes that are less hindered than aromatic groups.

We could install aromatic groups and alkyl groups onto these alkanes to increase their visual activity. These reactions can simplify the synthesis of bioactive compounds, such as compound 10, which belongs to a family of narcotics. This model allows us to access intermediates selectively using static control.

By manipulating the groups on intermediate A, we can form a compound with a β S bond. This compound can undergo a bitter hydro elimination to produce an almar. This process could potentially result in a trice up to. The same strategy can be applied to other compounds.

If you manipulate the groups and perform a β hydro elimination with a beer in this case, you will obtain the L kin branch that can be summarized to the trice LK. The goal is simple: to achieve this transformation.

We attempt to simplify the transformation of monosubstituted alpha elephants by reacting them with an electrophile to access tri- or tetrasubstituted products in a single step. This process involves a regioselective Heck-type reaction for bi-substitution that remains stereocontrolled. Our collaboration includes working with Professor Theist at Texas A&M University.

We have calculated computations to determine the steps that result in high activity. The stereodetermining step involves the insertion of a Nickel species onto the ach bond to avoid static repulsion between the energy ligand and the X step ligands on the Nickel center. This ch insertion is stereoselective. By rotating the CC bond, the carbon Nickel bond and the π bonds and π orbitals can align in a way that allows for stereo retentive summarization to occur. This species will then undergo reductive elimination to form the final product. This summarization process is unique compared to existing routes and showcases the potential of our work.

Different types of Alkins, such as Alkins trub Alkins and Tetra alkins, can be accessed in good stereo activity despite being asymmetrical. High selectivity is not achievable compared to tr subs due to the lower energy difference between competing Transition states. However, purification of these ez isomers can be done through simple chromatography. The scope of products that can be made includes bo sub to our kins, utilizing the Klement strategy in addition to existing methods such as reactions or metasis reactions.

We extended these processes to selective reactions by working with the group of SUS IO in China. We use two symmetric energy carbon ligands to promote site-selective carbon reactions.

Access the single tumor of the carbon LQ Nickel species is necessary. Function the carbon Nickel bond to install different functionalities and create compounds in a high-enriched fashion. This process allows for the production of various products through selective couple function organizations. By functionalizing and activating alkanes, one can generate highly selective inter internet alkanes, including unactivated alkanes. While cyclic alkanes are less efficient, there is one example where internal alkynes can be used.

The process is ongoing and will be further developed. In addition to unactivated LKS, we can use Hector atom sub to Alkanes to create stereo centers relevant to bioactive compounds. We have developed a class of carbon nickel complexes that can be used to access various compounds through the development of reactions, including tandem transformations.

Functionalization is a key process in selective synthesis for creating various compound libraries. These libraries can be used to produce bioactive compounds of interest. The different versions generated through functionalization are both highly interesting and useful. We have recently summarized these versions in a review that we wrote.

Summary: In addition to utilizing Nickel chemistry, we also focus on iron chemistry for Multicomponent cross coupling reactions. This allows us to create valuable compounds, including bioactive molecules, as outlined on the Slide.

Before I end my talk, I want to acknowledge the hard work done by my students, postdocs, and collaborators, both past and present. We have worked together on understanding our reactions, and I want to thank the funding support from Singapore and other monetary awards from different agencies. Thank you.

Thank you very much MJ for a fantastic talk. Any questions from the audience?

When developing three-component reactions, a common pitfall is cross coupling between the electrophile. To address this, we typically use 2 to 3 equivalents of reagents to minimize side products resulting from homo or cross coupling. SP2 hybridized electrophiles tend to work best in our reactions, while SP3 hybridized electrophiles have been more challenging due to multiple side reactions.

In our first-generation reaction system, we used a bimetallic Nickel precatalyst for its efficiency and selectivity. Later studies showed that Nickel zero complexes can also be effective with larger carbon ligands, eliminating the need for sensitive Nickel one complexes.

When using Nickel zero complexes, the starting catalyst is Nickel zero, while Nickel one complexes go through a different activation process. EPR studies support this, although concrete proof is lacking due to the inability to isolate intermediates.

We are currently working on gaining more insights into the mechanism of the reaction. By using EPR studies, we have observed signals that suggest the generation of paramagnetic species like Nickel one or Nickel three. We believe that the Nickel zero N two cycle is dominant, but we cannot rule out Nickel one N three. Our calculations and PR studies support this hypothesis. We are still working on crystallizing the intermediate species to confirm their presence. Thank you for your attention. Next, we will have a demonstration of science of synthesis before introducing our next speaker. Science of synthesis is a comprehensive reference resource for synthetic methods, covering various types of organic and metallic compounds. It provides critical insights and practical advantages of different methods, making it a valuable tool for planning synthesis and exploring new areas. The content is organized into volumes based on product type and includes titles focused on emerging technologies in organic synthesis. You can explore the content through browsing, indexing, and searching tools on the website. Thank you for your interest, and we look forward to sharing more content with you in the future.

You can read the review by clicking on the arrows to move to the next section or download the entire PDF of a contribution. This particular article is from the Base Metal Catalysis volume, and other chapters from speakers Tatsuhiko Shino and Shan Liu are also available for free for webinar attendees for the next few days. Links to access these articles can be found in the chat window. Thank you for listening. Take the opportunity to try out synthesis in the coming days and contact your library for more information or trial access at your institution.

Naohiko will now introduce the next speaker, a professor from Hokkaido University. He obtained his PhD in 2014 from the University of Tokyo and worked as a postdoc at Stanford University before becoming an assistant professor at Hokkaido University. He is currently an associate professor with research interests in ch Functionalization and Asymmetric catalysis. He has pioneered the development of CP st about Catalysis and its in antis selective variants over the last decade and received the Chemical Society of Japan award for young chemists in 2021.

The talk will be on high variant cobalt catalyzed anti active stage activation enabled by chiral carboxy gases. Thank you for the kind introduction and invitation, Professor Yosi. The time is limited, so let's begin. Today, the topic is hybrid covert characteristic for character sheet activation.

Functionalization has been a hot topic in Organic Synthesis for the past two or three decades. Functionalization reactions can enable the synthesis of natural products and complex molecules from readily available starting materials, potentially changing the logic of synthesis. There are several strategies to create unreactive CH bonds, including radical reactions and nitrocarbon reactions. Our group is focusing on reaction development based on CH activation using transition metals, specifically in PC H activation. This process generates organometallic species from CH bonds to facilitate CH bond functionalization reactions.

There are several strategies to enable a specific type of reaction, with the most successful being direct C-H activation chemistry. In this approach, a directing group, such as a coordinating group like Ping ying or a carbon group, coordinates with a transition metal catalyst to facilitate cleavage at the β or γ position relative to the directing group. This enables the C-H bond to be cleaved, forming an ac bond and allowing for further reactions under specific conditions. This groundbreaking work was reported in 1993 by Professor Murray at O University, leading to the development of numerous reactions based on this directed C-H bond activation.

Generally speaking, there are three kinds of transition methods for cleaving the CH bond in CRE. One method is the rot method, which cleaves the CH bond via state variation. The second method is the electrophilic method, which activates the CH bond through a constructed metal de mechanism. The third method is the mono meter type reaction, often utilized with diesel methods. Among these methods, we prefer the second method, electro activation, with a focus on CP star Cobalt, rhodium, and iridium.

The metal catalyst has a variable metal center. It is generally stable to air and moisture, making it compatible with oxidizing reaction conditions. In many synthetic reactions, functionalization reactions are often oxidations. It is interactive and compatible with transition metals.

This threshold is an important seminar work by Professor Sam Mira at Oak University in 2007. They reported the use of CP steroid catalyst for direct she model activation. Since this report, numerous reactions have been developed using the CP steric catalyst, making it one of the most successful catalysts in she activation chemistry. However, the problem is that Clear hetero is too expensive. Currently, the price is somewhat high, but it is still one of the most precious transition metals.

Some people want to use cobalt, cobalt cha, and CH Activation as a meal.

Professor Yoskar is a pioneering figure in the field of Cobalt CCH Activation, having studied the activation for more than one decade. He introduced the use of a generative cobalt catalyst derived from a Cobalt source and a linear reaction to another reductant. This catalyst can facilitate various types of CH Activation based on its background in medium and iridium chemistry.

Our research in this area began almost 10 years ago, focusing on the chemistry of CP star cobalt Catalysis. This particular catalyst is unique and differs in reaction mechanism from traditional cobalt chemistry. For example, we have observed CH addition reactions to both alkene and enone substrates.

One division reaction was realized in the next year. After these works, CP Star Cobalt Catalysts have been widely used in the field of GH Activation and GH Functionalization for Organic Synthesis worldwide. Many groups have developed various reactions mimicking and realizing the unique reactivity of cobalt. Today, the focus will be on selective reactions using these Catalysts.

The CP star or C PC P type of regions always occupy the most coordination sites for the metal center. It is almost impossible to introduce chiral hosting chiral or other chiral ligands that are used in many other transition metal catalysis. One successful way to realize selective reactions is the introduction of chiral CPR Krema Group, which pioneered the design and synthesis of these chiral CPR Catalysts.

Many other groups have developed their own Cairo cp rhodium, iridium, and cobalt catalysts after this work. These catalysts have been successfully applied in various cat functionalization reactions involving cobalt. In 2019, Gramas group reported the use of these types of Co CP cobalt catalysts. They also provided the catalyst for Enio activation via C one activation.

In these cases, the catalyst exhibits activities after C activation. Our strategy for insertion is slightly different.

Chiral carboxylic acid or a chiral carboxylate is used for angio C one to collate. During activation, CP symmetric catalysis ch one to cleavage proceeds via a constructed meter. The proton mechanism, known as the cmed mechanism, involves the coordinating carboxylic acid working as a base to remove the proton without changing the oxidation state of the metal center, resulting in a metal cycle intermediate.

By introducing a chiral carboxylic acid, enantio ch mode cleavage can be achieved. The determining step in this process is ch mode activation. This strategy has been successfully utilized in para chemistry, where Professor Jin has used various groups to achieve excellent reactions based on this approach in selective ccied mechanism.

In paradigm chemistry, a BNT anionic ligand is used because a paradigm has full coordination sites. However, for CP symmetric catalysis, the complex only has three available coordination sites, with two already used for substrate carboxylic carboxy. An ion can only coordinate in a monodentate fashion to the metal, making the conformation very flexible and ruling out the use of a bidentate Riggan.

Therefore, a specific design for the chiral carboxylic acid is needed. A pioneering study by S group in K reported the CH amidation using CPW valid and the territory cut to derivatives.

They achieved selectivity, but it is not very high. This is the only example where we started our chemistry with CH activation based on this background. Our group has developed Chrobak acid tuned for combination with CBS star Cobalt and Rhodium Catalysis.

In many cases, we use volume catalysts and cobalt catalysis for Enio to ch functionalization. Today's topic is basement catalysis, focusing on examples using CP type cobalt complex and chiral carboxylic acids.

Today, I want to discuss the SP3 CH amidation of tauride using cobalt catalyst. This reaction was first reported by Dixon et al. in 2017. SP3 CH activation by CP symmetric catalysis is a challenging area in the field of functionalization. While most people use para-methoxybenzoic acid, this example demonstrates that a CP star cobalt catalyst can also be used for SP3 C functionalization.

In our investigation, we used carboxylic acid and cobalt. We tested many carboxylic acids but found it difficult to achieve high enantioselectivity with complex structures. Ultimately, we discovered that simple amino derivatives could work for this reaction. Chiral carboxylic acids are typically used in chiral palladium catalysts, but we used them for this special functionalization.

After extensive screening, we determined that hydrogenated bhdl is the best choice in terms of selectivity and reactivity.

Finally, we chose the Cata coach catalyst. We decided not to use the chiral cobalt due to its complicated synthesis. Instead, we opted for a simple tuning of the substitute group, which resulted in the major group being substituted with a methyl group. Although the reactivity decreased, the activity improved. This strategy, in comparison to chiral CP Riggans, is considered more effective. The tuned chiral CP Riggans can be easily synthesized through a classical cyclization route, as shown here.

We chose the reaction conditions based on improving reactivity and achieving an acceptable yield. The solvent was selected to enhance the reaction and angios activity. There is room for improvement in terms of selectivity. The molecular series showed compatibility with various α V and α A groups. However, reactivity and selectivity slightly dropped and we may need to consider changing the Dixon.

The Diao dioxazolone is a highly reactive precursor in the Functionalization reaction using CP star cobalt to rhodium and euric Catalysis. This substance can be changed to introduce various amide substitutes. The synthesis of CP start Catalysis is cheap and easy, and aminos are easily available. The reaction can be easily scaled up to Gram scale, with good yield and activity even in a gramscale reaction. The products can be converted to the corresponding amide or amine by nuclear Reduction, and the amide can also be transformed to aldehyde by partial Reduction.

This type of videoing books is particularly useful for synthesizing many other chiral compounds.

The amino acids work well for the α benji or α a substituted tauride in cases with α aide electro activity. We screen for this substrate and developed a new kind of chiral catalyst called Ferro and chiral carid. Ferrocene is a famous and excellent backbone for the development of chiral catalysts. Chiral Carboxylic Acids can be synthesized from commercially available and easily accessible chiral Oxin substituted to ferrocene via Diaco sed activity duration, brominated. By partially hydrolyzing the oxin group, various re groups can be introduced through standard coupling reactions.

After screening several kinds of Ferro and Chiral Carboxylic Acids, we found that the 35 tbu substituted Ferro and carboxylic acid was the best, although there is room for improvement in terms of activity.

The substrate is screened briefly and shows moderate energy activity, which is maintained in the presence of various sub duty joint. The reaction can proceed at four degrees. The reactivity is very high in this case, but it is difficult to identify the reason for the reaction. However, the reaction proceeded under very mild conditions.

The reaction mechanism involves the coordination of t to cobalt and carboxylate, creating the V ID mechanism to form an intermediate metal cycle. This process should be irreversible. The dioxins, metal, and CO2 are released during this step, with some conversion to Nitroso formation to form a bond with the intermediate. Protonation then produces the final product and regenerates the catalyst.

This is a brief summary of the fast activation of ch one using chrobak acid.

In the remaining time, I will discuss the recent results for the construction of the chiral sulfur center. Compounds such as su form, sums form, form amid, and other sulfur compounds are of interest in drug discovery and medicinal chemistry. These structures are also studied in organic synthesis. Recently, they have gained attention in drug discovery and synthetic chemistry.

Nitrogen can work as a directing group for CH activation. Various types of CH functionalization have been reported, including electroselectivity and desymmetrization reactions. A recent report describes a Demeter-type CH calculation cyclization using a chiral R catalyst. Professor BFC also reported the use of chiral carboxylic acid combined with the Ruen catalyst for a similar reaction. This rum has a structure similar to the CB star rhodium and cobalt catalysis. Based on this, we developed the Shang circular CH amidation reaction using cobalt catalysis and chiral carboxylic acid.

To promote the second cyclization in this case, we need to heat up the reaction mixture and add acetic acid. We obtained a chiral center when we screened a suitable catalyst.

We found that the pseudo 32 symmetric Chiral carboxylic acid was the best. This type is our second generation of Chiral carboxylic acid, known as gen two. This generation is faster by fixing the carbon two carbon. The dihedral angle can be fixed, and the symmetry can reduce possible conformations.

Furthermore, we found that the hydrobin backbone is slightly better than the bin after backbone. We achieved a 96% yield for this reaction.

The pseudo C2 chiral carboxylic acids can be synthesized from a di-bromo compound via double addition of acetic acid. The group can then be removed to show the substrate's tosco and various types of bin benty. These oxides are easily accessible, with moderate quality, and substitutions can be made by changing the dioxazolone.

We can introduce a E for heteros students. Good activity can be found from 9 to 3. I can briefly show the Summary Mechanistic studies in most cases.

Fast rejection of the reverse reaction of the CH activation occurs when the reaction is run in the axon. By using a two Prosvent, we observe some HD exchange in the positional order. The cleavage is naturally reversible. However, when we add di di to the reaction mixture, the starting material does not contain deuterium at the orbital positions. This indicates that in the presence of the reactants, one cleavage is almost irreversible. After one cleavage, the reaction with the Dixon is much faster than the protodemeter in the reversible CH activation.

We check the Kie and open up the 3.29. The C one cleavage is already determining. This is the Catalytic Cycle. It is almost the same as the previous one, with the key point being activation.

We use a saving mechanism to determine both the step and rate determining step. Through DFT studies, we have reduced the Activation Transition states model. By using GFTH and the correct program, we can obtain representative confirmations. These tools are helpful for organic chemists in identifying large transitional state structures.

In the first transitional state for the major enantio, we observe π bond interaction between the re group and the substrate Switch bonds. In the minor transitional state for the minor enantio, there is no clear R CHP bond interaction, which may affect the order of the goods activity. This is a second summary, where we also realize selective synthesis of benzo DN in one site using a cobalt catalyst.

All the work was completed in the finance department at Kaido University. I spoke with three students today who are majoring in chemistry. I am grateful for their hard work and dedication, as well as that of other students.

This is to acknowledge receipt of the J SBS Japanese grant. Thank you for listening.

Thank you for your talk. Let's move on to the Q&A session. Yan Shell has a question about the role of molecular sheeps in reactions. The molecular sheeps can increase reactivity by absorbing or dissociating acetonic from the precursor. They can also coordinate with the substrate reagent and generate unsaturated species. The best molecular sheep for this reaction is IOC CS X.

Regarding directing groups for SP3 CH activation, so far TA AMI is the only effective directing group for cobalt catalysis. We are working on expanding the scope of directing groups, but it is a tough challenge.

We have introduced different carboxy acid skeletons, with the pseudo C2 asymmetric one being effective in some cases. The effectiveness of the catalyst depends on the substrate structure.

In DFT calculations, we observed important π-π interactions in the CH activation step. The electronic effect does not have a significant impact, but bulky substitutions can affect the reaction.

Introducing bulky groups on the Ru group can lower the activity of the reaction.

If there are no more questions, I will close the talk. Thank you for your participation. Next, we will hear from Professor Zhang Lu from Zhejiang University.

He obtained a bachelor's degree in 2003 and a PhD in 2008. After spending some years as a Post of public education and T CPU at the University of Wisconsin-Madison, he returned to his alma mater in 2012 and was promoted to Professor in 2018. He is primarily engaged in researching Asymmetric iron and cobalt para based on novel cle design, resulting in numerous published papers and filed patents on this topic.

Today, he will discuss his research on iron and cobalt chemistry. Thank you for the kind introduction and invitation. My talk will focus on Asymmetric iron and cobalt cites. In nature, biological organisms utilize 3D metals and their surroundings to achieve specific functions.

Modern industry heavily relies on pressure metals, highlighting the need to design catalysts with 3d metals to ensure sustainable catalysis. My research focuses on selective catalytic hydrogenation and hydro functions of various compounds. This reaction is widely used in academia and industry, with around 10 million tons of compounds produced through hydrogenation.

The organic silicon industry spends approximately 5.6 tons of platinum per year. However, the majority of platinum used has not been recycled. The industry heavily relies on pressure metals with phosphine ligand to achieve high selectivity in the transformation process.

The functional group is typically introduced to the unsaturated substrate. However, due to weak electronic and steric effects, the functionality of the resulting metal complex is dependent on the CD Z CD D model. Therefore, achieving highly selective transformations of these substrates remains challenging compared to noble transition metals.

The application of 3D metals is still limited due to poor reactivity and selectivity. Low covalent 3D metals easily lose electrons, weakening the D orbital's ability to accept electrons from π bonds. The volatile balance of spins and coordination models makes it difficult for D electrons to fill back into the π* bond. Small atomic radius can lead to ligand dissociation, further decreasing reactivity and selectivity. Our strategy is to use a design strategy to control selectivity.

Our main research funding is focused on utilizing readily available study material to produce high-value products.

The power design has three parts: the synthesis of a novel cut ligand for iron and cobalt. The water cut refers to a chiral, unsymmetric tree density ligand that we call the cut. We aim for this ligand to mimic the water set and be able to cut various substances to produce high-value products.

Part two discusses the coordination model and the valence state of metals. Part three covers the sequential reactions in the program.

The challenge of creating asymmetric 3D metal catalysts lies in the shortage of suitable chiral catalysts and the lack of natural design rules to follow. To address this, we utilized a tree containing multiple ligands to stabilize the metal complex. By introducing the redux non-innocent property, we were able to facilitate electron transfer and stabilize the metal complex. Additionally, the introduction of an unsymmetric skeleton allowed for more variations in the catalyst. Our concept involves utilizing a tree-like density coordination with redux non-innocent properties and an unsymmetric skeleton. Following this concept, a series of colored ligands were synthesized.

These complexes can be combined with metal salt to scale up the model synthesis to gram scale. The resulting product is suitable for library building. The metal complexes can be reduced to low valent metal hydrides using either hydride or base.

The low val measure of hydrated metal is unstable and difficult to modify by Nmrox ra structure. The only method we use is E pr combined with computational study. Through our research, we have found that a full coordinate iron hydrate species may be formed. The computational study also suggests that the coin state is more stable than the double state, leading to MLCT occurring to stabilize the low val 3d metal. This metal hydride species could react with other regions, such as cylin, to form metal cylin species following a regular coordination model and the value of metals. Let's first discuss the cobalt one species.

We want to use cobalt low val 3d metal species to solve the challenge problem. The pressure metal cannot solve this problem. The one issue in Asymmetric Hyden generation so far is the easy mixture of our kings.

Professor Anderson wrote a review stating that asymmetric hydrogenation depends on the configuration of the starting material. If a mixture of our kin is used, the energy convergence reaction can only occur using the chelating group without a king group. Achieving the convergence of reactions is quite difficult. An example from literature in 1993 showed that Steve Buck used a Titanic test to test the mixture of our kin, but the product had poor ee. Additionally, obtaining the minimal function of our gene is also difficult, requiring harsh synthetic conditions or multiple synthesis steps. However, obtaining the mixture, olive, is relatively easy, although many might consider this mixture to be wasteful.

We believe that we can use this waste to produce a high-value product. In short, we have successfully achieved the Cobo COCA as an Asymmetric hygienic and easy mixture of our genes.

The gramscale reaction can be carried out smoothly. The methyl group is the other possible position. It is important to mention that a catalytic amount of saline is necessary to achieve this.

Our methodology can be used to synthesize a variety of natural products. The study material can be obtained through methods such as greener addition to ketones or the free FK reaction using LQ with aromatic compounds. We are also interested in the mechanism, so we propose to determine that the terminal alkene in carbohydrate species may be generated by isomerization reactions.

The cobalt species is in an open shell single state and is supported by computational study. Our primary research question is that the cobalt intermediate is a key intermediate. It can undergo a σ bound meta with xylene, which is more favorable than with hydrogen.

We added a catalytic amount of cyle so that the coal yne could be converted to the corresponding carbohydrate species.

The spin state of the intermediate changes frequently, allowing the reaction to occur. Previously, a high and anti-selective reaction was achieved using a mixture with a Chating group. Our search involves summarization, but it should also consider the thermodynamic disadvantage.

But this Russia could occur smoothly.

The isomer reaction can be used with different substrates to solve issues that pressure metal cannot address, such as the migration of dye. Through our experiments, we discovered that entering one aerobic species is more stable than entering three aerobic species, resulting in the migration over two carbons. In our specific scenario, the migration occurred over 11 carbons. In our mechanistic study, we identified the primary RQ Cobalt species as a key intermediate. We then considered introducing different atoms, such as boron, which could potentially produce the desired outcome and lead to various functional groups. Using our color ligand, we observed that the reaction could proceed smoothly even when using a mixture, demonstrating its synthetic utility.

We conducted a census of an intermediate compound found in nature. In the literature, three primary metal catalysts were used: iridium, Luthi, and planum. The process involved eight steps and yielded 5% using their strategy, compared to our strategy which only required four steps. We were able to deliver the product with 70-67% ee.

In our previous discussion, we talked about the cobalt species. Now, let's consider the iron species. This species differs from the cobalt species. In our previous study, we successfully achieved the IOC catalyzed Asymmetric hydration, but the Hydrosport was unsuccessful. For example, reports of Asymmetric reduction reactions using iron catalysts have shown that even with pressure metals, the selectivity is not very high.

We are grateful to Professor Nikonov for highlighting our work and giving us credit. He referred to this catalyst as "lo Carol."

but they still have a problem.

Achieving an anti-selective hydrogenation is a longstanding challenge in hydrogenation reactions.

Professor Zhang Xiu reviewed the lack of successful results in using irony tests for Asymmetric hygienic of kings. Professor Paul attempted to achieve antis selective hygienic using diphosphine, but encountered issues with ligand dissociation. Two additional problems were identified: the iron fish undergoing β hydro animation to produce three subs alkene, inhibiting the reaction, and the difficulty of al Q I iron species undergoing σ bond metas to generate the cataline. In response to these challenges, three strategies were implemented.

We used a large ligand to inhibit ligand dissociation. Additionally, we introduced a weak coordination ligand to inhibit isomer reactions. A highly active hydrogen species, such as Cyle, was also introduced to accelerate σ bond metastasis. As a result, we successfully achieved iron catalyzing the asymmetric hydrogenation of our ketones. This protocol can be applied when synthesizing compounds related to our ketones.

with three substitute outings.

We found the mechanism quite interesting and discussed it with Professor Yong Guizhou in the IC P. He suggested using hydrate the shuttle to code the hydro cylinder, which plays a role in generating the active metal species. People often ask if we need to use the arrow to achieve high energy selectivity, including the 11 die arrow and 11 dot RQ sub to the elephant. One of my undergraduate students should be appreciated for doing a lot of screening as an undergraduate and finding that a larger ligand could increase selectivity and reactivity.

The product can be guided with full conversion and 92% ee. Compared to the metal, one species has a different coordination model than the metal two species.

Using coal, we aim to solve a challenging problem based on what we have learned from literature. Many groups have reported our kin migration and functionalization using various metals and functional groups. However, the NN two selectivity reaction remains a challenge. With our method, the A K migration and hydroponic reaction can smoothly produce a product with 99% ee, with Cobalt two hydro species playing a key role.

Not only could the insertion migration reaction occur, but the cobalt two species could also exhibit 3D metals properties to undergo the hat reaction and produce a radical. In our case, the hydroamination of simple R king could provide the Cairo amine with 86% ee. During the magnum study, we discovered the radical intermediate.

The coal hydro species pathway was compared to the literature results. The best results from literature were found in 2009, when Professor Wander Hof used a gold catalyst with a metal national intermediate to achieve a product yield of 78%. Our radical strategy has proven to be a successful method for achieving radical ligand reactions. The next step is to control the program for sequential reactions.

If you want to achieve the desired product using our catalyst, there are two steps involved. The first issue is the selectivity of the reaction. The second is the compatibility of the catalyst. To address the selectivity issue, we use divers, Veron, and hydro Cyl to produce the linear product. When using Catalan, we are able to obtain branch products with high yield and efficiency. It is important to note that coal CC species were observed in this process, but we do not want these species as they only produce a specific product. We are aiming for a different type of product.

When the balance of cobalt shifts from one species to another using an ionic ligand, the branch product can be opened smoothly. For example, we can insert our kind into the cobalt hydrate species with nickel-type selectivity. Then, a new electron fire can be added, such as boron and proton, to produce the corresponding product. People may wonder how to define the cobalt binding species, so we changed the A B ligand.

Using cyle as a reagent inhibits the reaction. In this experiment, both the cobalt one carbohydrate and the cobalt cell are present. However, the cobalt cyne is more favored, so we are attempting to resolve the compatibility of the catalyst.

The ideal example is using the catalyst to achieve two reactions called multiple functional ky. Our O IP O IP ooiqal ligands occur smoothly to produce the chiral cline, boring, and amine product. When one catalyst did not work, we put two catalysts together.

One example is shown to demonstrate how combining the phosphine ligand with the Nitro ligand can result in Beyle selectivity. The full product can be obtained using different methods of separation.

In some cases, two cats will fight each other. The first catalyze is put in the direction, then the next ligand is added to the Russian system. The next ligand can take the metal from the formal Cali, causing the formal callus to die and allowing the new cala to work well. This strategy allows for the synthesis of a variety of van cell and nitrogeno. We are interested in both fundamental research and applications. The asymmetric transformation of B of chemicals, such as one P 10 all kinds, the AAA sign, and propine, can undergo corresponding reactions to deliver the Croyle or chiral amines.

These new monomers can create polymers with unique properties. In summary, this is a quick overview.

Our associate is tasked with finding a special ligand suitable for iron and coal, and determining the relationship between structure and reactivity. This ligand has been used by other groups with different metals like platinum and palladium.

I want to thank my students, collaborators, and the funding support. I also want to thank the audience and am happy to answer any questions. Thank you, that's all.

I want to thank my students, collaborators, and funding support. I also want to thank the audience for being here and I am happy to answer any questions. Thank you for sharing your chemistry with us. The lecture is now open for questions. Does anyone have any questions?

It seems that you have developed neutral tridentate ligands and ionic tridentate ligands. Is this chemistry specific to cobalt hydride?

Yes, the nature of the ligand controls the valency of the cobalt species. The reductant used does influence the oxidation state of cobalt and iron species. We have done CV to detect the reduction of the ligand, but it is difficult to determine the relationship between the metal balance and the reductive properties of the ligand.

You mentioned cobalt two hydride and hydrogen transfer. Is this always the case for cobalt two hydride?

It is a unique case because the cobalt one hydride species typically cannot undergo the hydrogen atom transfer reaction. Our proposed ligand has non-reductive properties which allow for MLCT to occur, converting cobalt two to cobalt three for smooth hydrogen atom transfer.

For your neutral ligand design, you promote a cut-type ligand unsymmetrical structure. How does this impact desired reactivity compared to classical P-box type ligands?

We have observed differences in the asymmetric reaction compared to classical P-box ligands. P-box ligands are suitable for loose acid catalysis, while our O-IP type ligands catalyze reductive reactions effectively.

If there are no further questions, I will close the lecture. Thank you to all the speakers and participants for joining us. Keep an eye out for future topics in the Ti WebCheminar Series. Thank you for attending and have a great evening and weekend. Goodbye.