Steric-switched defluorofunctionalization selectivity: controlled synthesis of monofluoroalkene-masked medium-sized heterocyclic lactams and lactones  

作　　者：Hao Zeng Hengyuan Li Huanfeng Jiang Chuanle Zhu 

机构地区：[1]School of Chemistry and Chemical Engineering,Key Lab of Functional Molecular Engineering of Guangdong Province,South China University of Technology,Guangzhou 510640,China

出　　处：《Science China Chemistry》2022年第3期554-562,共9页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China (21702064);the Guangdong Basic and Applied Basic Research Foundation (2020B1515020012)。

摘　　要：The steric-switched ipso-defluoroamination-triggered and ipso-defluorooxylation-triggered cyclization of(trifluoromethyl)alkenes with amino alcohols and diamines are achieved under mild conditions. This regioselective strategy distinguishes the different nucleophilic heteroatom sites in amino alcohols and unsymmetric diamines by the sequential defluorinative functionalization of two C(sp^(3))–F bonds in a CF_(3) group. Various attractive monofluoroalkene-masked medium-sized heterocyclic lactams and lactones are obtained in moderate to excellent yields. Simple derivation of these masked-heterocycles efficiently affords useful skeletons of lactams, lactones, and 1,4-oxazepanes in a single diastereoisomer. Mechanism studies indicate that a unique sequential ipso-/γ-selective defluorinative functionalization pathway is involved in these transformations.

关 键 词：switched-selectivity C–F bond cleavage medium-sized heterocycle LACTAM lactone 

分 类 号：O621.25[理学—有机化学]