Stereodivergent Alkylation of Unstrained C(sp <sup>3</sup> )─C(sp <sup>3</sup> ) Bonds
Abstract
Abstract Asymmetric functionalization of C─C σ bond is a straightforward way to edit molecule backbones but heavily relies on strained rings. The related process with unstrained structure is highly challenging, and only several cases are reported. However, these examples can just achieve related enantiomers through C─C σ bond activation. The stereodivergent C─C σ bond functionalization for precise access to all stereoisomers is unknown. Here we have established two catalytic systems to show the feasibility of unstrained C─C σ bond functionalization as an efficient pathway in stereodivergent synthesis. Both unnatural amino acid derivatives bearing two vicinal stereocenters and carbonyl compounds containing a tertiary fluoride are constructed in good yields with high diastereo‐ and enantioselectivities. Stereodivergent access to all these chiral skeletons is demonstrated possible with simple dictation of ligand configurations. Mechanistic studies unveil the resolution pathway of racemic allyl substrates through diene formation instead of typical metal interconversion and C─C formation as rate‐determining step.
Article Details
Authors (4)
Yang Liu
Bi‐Cheng Deng
State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Shanghai 200032 China
Li‐Hong Xiong
State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Shanghai 200032 China
Zhi‐Tao He
School of Chemistry and Materials Science Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences Hangzhou 310024 China