Site- and Stereoselective C(sp3)-H Borylation of Strained (Hetero)Cycloalkanols Enabled by Iridium Catalysis

被引：25
|
作者：
Gao, Qian [1 ,2 ]
Xu, Senmiao [1 ,2 ]
机构：
[1] Chinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China
[2] Univ Chinese Acad Sci, Beijing 100049, Peoples R China
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2023年 / 62卷 / 08期
基金：
国家重点研发计划; 中国国家自然科学基金;
关键词：
Asymmetric Catalysis; C-H Activation; Chiral Bidentate Boryl Ligand; Cycloalkanols; Organoboron; C-H FUNCTIONALIZATION; DIASTEREOSELECTIVE SYNTHESIS; CARBOXYLIC ESTERS; CYCLOPROPANATION; ACTIVATION; ARYLATION; CARBON; CYCLOBUTANES; TERTIARY; SILYLATION;
D O I：
10.1002/anie.202218025
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Transition metal-catalyzed site- and stereoselective C-H activation of strained (hetero)cycloalkanes remains a formidable challenge. We herein report a carbamate-directed iridium-catalyzed asymmetric beta-C(sp(3))-H borylation of cyclopropanol derivatives. A variety of densely functionalized cyclopropanols were obtained in good enantioselectivities via desymmetrization and kinetic resolution. In addition, site-selective C(sp(3))-H borylation of methine groups furnished alpha-borylated (hetero)cycloalkanols in moderate to good yields. The synthetic utility of the method was further shown in a gram-scale synthesis and diverse downstream transformations of borylated products.
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页数：7
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