Asymmetric, Remote C(sp3)-H Arylation via Sulfinyl-Smiles Rearrangement

被引：0
|
作者：
Hu, Yawen [1 ]
Hervieu, Cedric [1 ]
Merino, Estibaliz [2 ,3 ]
Nevado, Cristina [1 ]
机构：
[1] Univ Zurich, Dept Chem, Winterthurerstr 190, CH-8057 Zurich, Switzerland
[2] Univ Alcala, Fac Farm, Dept Quim Organ & Quim Inorgan, Inst Invest Quim Andres M Rio IQAR, 28805 Alcala De Henares, Madrid, Spain
[3] Inst Ramon & Cajal Invest Sanitaria IRYCIS, Ctra Colmenar Viejo,Km 9-100, Madrid 28034, Spain
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2024年 / 63卷 / 17期
基金：
瑞士国家科学基金会;
关键词：
Sulfinyl-Smiles Rearrangement; Hydrogen Atom Transfer; Asymmetric Remote Arylation; Photoredox Catalysis; alpha-Arylated Amides; C-H FUNCTIONALIZATION; RADICAL TRIFLUOROMETHYLATION; BOND FORMATION; STEREOSELECTIVE-SYNTHESIS; PHOTOREDOX; ALKYLATION; ALKENES; AMINES; TRUCE; CYANATION;
D O I：
10.1002/anie.202319158
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
An efficient asymmetric remote arylation of C(sp(3))-H bonds under photoredox conditions is described here. The reaction features the addition radicals to a double bond followed by a site-selective radical translocation (1,n-hydrogen atom transfer) as well as a stereocontrolled aryl migration via sulfinyl-Smiles rearrangement furnishing a wide range of chiral alpha-arylated amides with up to >99 : 1 er. Mechanistic studies indicate that the sulfinamide group governs the stereochemistry of the product with the aryl migration being the rate determining step preceded by a kinetically favored 1,n-HAT process.
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页数：7
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