化学
对映选择合成
铑
外消旋化
区域选择性
分子内力
轴手性
喹啉
手性(物理)
催化作用
复分解
阿托品
立体化学
药物化学
组合化学
有机化学
聚合
Nambu–Jona Lasinio模型
手征对称破缺
物理
聚合物
量子力学
夸克
作者
Panjie Hu,Lingfei Hu,Xiao Xi Li,Minghu Pan,Gang Lü,Xingwei Li
标识
DOI:10.1002/anie.202312923
摘要
Abstract Axially chiral open‐chained olefins are an underexplored class of atropisomers, whose enantioselective synthesis represents a daunting challenge due to their relatively low racemization barrier. We herein report rhodium(I)‐catalyzed hydroarylative cyclization of 1,6‐diynes with three distinct classes of arenes, enabling highly enantioselective synthesis of a broad range of axially chiral 1,3‐dienes that are conformationally labile (Δ G ≠ ( rac )=26.6–28.0 kcal/mol). The coupling reactions in each category proceeded with excellent enantioselectivity, regioselectivity, and Z/E selectivity under mild reaction conditions. Computational studies of the coupling of quinoline N ‐oxide system reveal that the reaction proceeds via initial oxidative cyclization of the 1,6‐diyne to give a rhodacyclic intermediate, followed by σ‐bond metathesis between the arene C−H bond and the Rh−C(vinyl) bond, with subsequent C−C reductive elimination being enantio‐determining and turnover‐limiting. The DFT‐established mechanism is consistent with the experimental studies. The coupled products of quinoline N ‐oxides undergo facile visible light‐induced intramolecular oxygen‐atom transfer, affording chiral epoxides with complete axial‐to‐central chirality transfer.
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