Recent Advances in Asymmetric Transformations of Unactivated Alkanes and Cycloalkanes through Direct C—H Functionalization  

作　　者：Shiyan Cheng Qianyu Li Xiuliang Cheng Yu-Mei Lin Lei Gong 

机构地区：[1]Key Laboratoryof Chemical Biology of Fujian Province,Collegeof Chemistry and Chemical Engineering,Xiamen University,Xiamen Fujian 361005,China [2]Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province(IKKEM),Xiamen,Fujian 361005,China

出　　处：《Chinese Journal of Chemistry》2022年第23期2825-2837,I0002,共14页中国化学（英文版）

基　　金：funding from the National Natural Science Foundation of China(grant nos.22071209,22071206);the National Youth Talent Support Program,the Natural Science Foundation of Fujian Province of China(grant no.2017J06006);the Fundamental Research Funds for the Central Universities(grant no.20720190048).

摘　　要：The direct conversion of unactivated alkanes and cycloalkanes into structurally diverse molecules through aliphatic C—H functionalization is a useful process, which has attracted intense interest from academia and industry. Methods to control chemo- and site-selectivity, combined with asymmetric catalysis, provide appealing access to high value-added enantiomer-enriched compounds but are far less developed. This review focuses on recent progress in (i) asymmetric reactions of alkanes or cycloalkanes with prochiral substrates which generate a stereocenter adjacent to the cleaved C(sp3)–H bond, and (ii) C(sp3)–H enantiodiscriminatory reactions creating a new stereogenic center on the carbon of a cleaved C(sp3)–H bond. Elegant strategies are discussed, including (a) metal carbene-induced C—H insertions by chiral rhodium catalysts, (b) metal-oxo-mediated C—H oxidation by biomimetic manganese catalysts, (c) enzyme catalysis by cytochromes P450 variants, and (d) dual catalysis by a photocatalyst and a chiral Lewis acid (CLA) or a chiral phosphoric acid (CPA). These catalytic systems can not only precisely recognize primary, secondary and tertiary C—H bonds at specific positions in alkanes and cycloalkanes, but also support a high level of stereoselectivity in the reactions. It is expected that the advances will stimulate further progress in asymmetric catalysis, synthetic methodology, pharmaceutical development and industrial processes.

关 键 词：Asymmetric catalysis C-H functionalization ALKANE SITE-SELECTIVITY ENANTIOSELECTIVITY 

分 类 号：O62[理学—有机化学]