We are interested in:

l Developing novel methodologies for transition metal-catalyzed reactions

l Deep studies into the reaction mechanism, which is the foundation for future applications of this chemistry.

Catalytic Arene Functionalization via π-Coordination

  Aromatic rings are among the most important functional molecule skeletons and are found widely in natural products, pharmaceuticals, and macromolecules. For example, nearly 80% of all global drugs bear aromatic rings. Therefore, the development of selective and efficient strategies for arene functionalization is a long-standing endeavor in synthetic chemistry. Since Hafner and Fischer synthesized the bis(benzene)chromium, a Cr(0)-complexed arene, which plays an important role in the development of organometallic chemistry in the 1950s, extensive studies on metal η⁶-arene complexes have been addressed. However, in contrast to numerous reactions of metal-complexed arenes that have been developed, only quite a few catalytic examples of arene functionalization via η⁶-coordination have been reported to date.

  My research team aims to design and develop catalysis using η⁶-coordination with transition-metalsthat provide novel methods for the synthesis and functionalization of aromatic compounds. We seek to provide strategically creative solutions through the development of transition-metal catalysts.

If you are interested in this part, please see (1) J. Am. Chem. Soc. 2020, 142, 3706, (2) J. Am. Chem. Soc. 2022, 144, 1144, (3) J. Org. Chem. 2023, 88, 20, 14264, and (4) Acc. Chem. Res. 2024, 57, 15, 2194.

Amine Synthesis and Asymmetric Catalysis

  We are also interested in the synthesis of chiral α-branched amines, which are common structural motifs in functional materials. pharmaceuticals, and chiral catalysts. The reported methods suffer from several drawbacks, such as harsh conditions, narrow substrate scopes, and the requirement of directing groups. Moreover, the control over absolute stereo-chemistry remains elusive in the reported methods.

  Therefore, our group focus on the development of an atom-economical, by-product free method to synthesise chiral α-branched amines in an enantioselective manner. Specifically, our strategy is based on the following elementary steps:

1) Ni-mediated β-hydride elimination of sulfonyl benzylamine to form sulfonyl imine in-situ

2) Ni-mediated oxidative cyclometalation of imine and unsaturated bonds (such as alkyne or alkene), followed by protonation, β-hydride elimination, and reductive elimination to afford the desired product.

  During the process, the amine could perform a dual role in a catalytic cycle by serving both as a precursor to the imine and as a hydrogen donor via hydrogen transfer, a formal insertion of an unsaturated motif into the α-C-H bond adjacent to the nitrogen atom of amine could be accomplished.

If you are interested in this part, please see (1) J. Am. Chem. Soc. 2021, 143, 4154, and (2) Nat. Commun. 2021, 12, 5881.