2025年4月1日，华东理工大学张志鹏小组在《美国化学会杂志》发表论文，宣布他们研制了吡啶-恶唑啉配体增强Pd（II）催化烯烃氨基乙酰氧基化非对称合成双芳基桥接7元n杂环和轴手性异构体。

研究了一类新的联萘基单位增强吡啶-恶唑啉配体，以促进pd催化的非活化联芳烯烃分子内7-外氨基乙酰氧基化反应。具有手性中心的双芳基桥接7元n -杂环具有优异的对映选择性（高达99:1 er）。对一系列联芳基桥接7元环的计算研究，通过杂原子、保护基和手性中心的取代基效应，深入了解了潜在手性联芳基单元的旋转势垒。外消旋轴手性双芳基的分子内对映选择性胺乙酰氧基化动力学拆分也已经实现，提供了以前无法获得的具有手性中心和手性轴的双芳基桥接7元n杂环，以及轴手性双芳基氨基醇。

附：英文原文

Title: Enhanced Pyridine-Oxazoline Ligand-Enabled Pd(II)-Catalyzed Aminoacetoxylation of Alkenes for the Asymmetric Synthesis of Biaryl-Bridged 7-Membered N-Heterocycles and Atropisomers

Author: Beibei Guo, Xiaoyang Yan, Zicong Wang, Chen Shen, Weifu Chen, Shouyi Cen, Qian Peng, Zhipeng Zhang

Issue&Volume: April 1, 2025

Abstract: A new class of binaphthyl unit-enhanced pyridine-oxazoline ligands was developed to promote the Pd-catalyzed enantioselective intramolecular 7-exo aminoacetoxylation of unactivated biaryl alkenes. Biaryl-bridged 7-membered N-heterocycles bearing a chiral center were obtained in good yields with excellent enantioselectivities (up to 99:1 er). Computational investigations on a series of biaryl-bridged 7-membered rings provided insights into the rotational barrier of the potentially chiral biaryl unit by the substituent effect including the heteroatom, the protecting group, and the chiral center. The kinetic resolution of racemic axially chiral biaryls via intramolecular enantioselective aminoacetoxylation of alkenes has also been achieved, affording previously inaccessible biaryl-bridged 7-membered N-heterocycles bearing both a chiral center and a chiral axis, as well as axially chiral biaryl amino alcohols.

DOI: 10.1021/jacs.5c00077

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c00077