文献类型：期刊文献

英文题名：Diastereo- and Enantioselective Synthesis of Eight-Membered Heterocycles via an Allylation/Ring Expansion Sequence Enabled by Multiple Catalysis

作者：Yang, Wu-Lin[1,2];Wang, Yuan-Lin[1,2];Li, Wen[1,2];Gu, Bu-Ming[1,2];Wang, Si-Wen[1,2];Luo, Xiaoyan[1,2];Tian, Bo-Xue[3];Deng, Wei-Ping[1,2,4]

机构：[1]East China Univ Sci & Technol, Sch Pharm, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Shanghai Key Lab New Drug Design, Shanghai 200237, Peoples R China;[3]Tsinghua Univ, Sch Pharmaceut Sci, MOE Key Lab Bioinformat, Beijing 100084, Peoples R China;[4]Zhejiang Normal Univ, Dept Chem, Key Lab Minist Educ Adv Catalysis Mat, Jinhua 321004, Zhejiang, Peoples R China

年份：2021

卷号：11

期号：20

起止页码：12557

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20214211041348);WOS:【SCI-EXPANDED(收录号:WOS:000709692900013)】；

基金：This work was supported by the National Natural Science Foundation of China (nos. 21901072, 21971062, and 22171082), the Tsinghua-Peking University Center for Life Sciences (no. 61020100120), and the Start-up Foundation of Tsinghua University (no. 53332201420). The authors thank the Research Center of Analysis and Test of the East China University of Science and Technology for the assistance with the HRMS and NMR analyses.

语种：英文

外文关键词：multiple catalysis; asymmetric synthesis; sequential reaction; medium-sized heterocycle; allylation

摘要：The development of protocols for constructing chiral medium-sized heterocycles with high efficiency and excellent stereocontrol is of great interest owing to their ubiquitous occurrence in natural products and biologically active pharmaceuticals. Nonetheless, current synthetic approaches are limited due to unfavorable enthalpy and entropy factors, as well as transannular interactions. The present work addresses this issue by designing an asymmetric allylation/ring expansion reaction of 2-(1- hydroxyallyl)phenols and cyclobutanone carboxamides enabled by sequential iridium/zinc/bifunctional squaramide catalysis, affording a series of 8-membered benzo[b]oxocines in high yields with high diastereo- and enantioselectivities. Mechanistic investigation reveals that the enantioselectivity is controlled by the chiral iridium catalyst, while density functional theory calculations demonstrate that the diastereoselectivity is controlled by the chiral bifunctional squaramide catalyst. Moreover, the sequential allylation reaction strategy is demonstrated to be also applicable to the synthesis of two types of enantiomerically enriched nitrogen heterocycles, 8-membered benzo[b]azocines and polycyclic cyclobuta[b]quinolines.