康 · 学术 | Reaction of the Day No. 1380

摘要：Collegeof Chemistry, Frontiers Science Center for New Organic Matter, NankaiUniversity, Tianjin 300071, China

转自：康龙化成

Catalytic Asymmetric Oxidative Couplingbetween C(sp3)−HBonds and Carboxylic Acids

Xian-MingLiu,# Fu Li,# Xiao-SongXue,* Li-Jun Xiao,* and Qi-Lin Zhou*

Collegeof Chemistry, Frontiers Science Center for New Organic Matter, NankaiUniversity, Tianjin 300071, China

—J. Am. Chem. Soc., 2024, DOI:10.1021/jacs.4c12544

Recommended by Chaoyou Liu _ PDM

Keywords: photo catalysis, enantioselectiveoxidation, functionalization of C(sp3)−Hbonds (反应类型),C(sp3)-O (成键类型), CuCl, NaBArF,Chiral BOX (催化剂),carboxylic acids, open-chain alkenes and alkynes (原料),chiral ester (产物),DTBP (其他)

ABSTRACT: Thedirect enantioselective functionalization of C-(sp3)−H bonds in organic molecules couldfundamentally transform the synthesis of chiral molecules. In particular, theenantioselective oxidation of these bonds would dramatically change theproduction methods of chiral alcohols and esters, which are prevalent innatural products, pharmaceuticals, and fine chemicals. Remarkable advances havebeen made in the enantioselective construction of C−C and C−N bonds through theC(sp3)−H bond functionalization. However, thedirect enantioselective formation of C−O bonds from C(sp3)−H bonds remains a considerablechallenge. Authors report a highly enantioselective C(sp3)−H bond oxidative coupling withcarboxylic acids. The method applies to allylic and propargylic C−H bonds andemploys various carboxylic acids as oxygenating agents. The method successfullysynthesized a range of chiral esters directly from readily available alkenesand alkynes, greatly simplifying the synthesis of chiral esters and relatedalcohols.

Overviewof strategies for enantioselective C(sp3)−Hoxidation. (A) Challenges of enantioselective oxidation of C(sp3)−H bonds. (B) Kharasch reaction.(C) Enantioselective oxidative coupling of C(sp3)−Hbonds with carboxylic acids.