Kinetic Resolution via Rh-Catalyzed C-C Activation of Cyclobutanones at Room Temperature

被引：76

作者：

Deng, Lin ^{[1
,3
]}

Fu, Yue ^{[2
]}

Lee, Siu Yin ^{[1
]}

Wang, Chengpeng ^{[1
]}

Liu, Peng ^{[2
]}

Dong, Guangbin ^{[1
]}

机构：

[1] Univ Chicago, Dept Chem, 5735 S Ellis Ave, Chicago, IL 60637 USA

[2] Univ Pittsburgh, Dept Chem, Pittsburgh, PA 15260 USA

[3] Genentech Inc, Dept Small Mol Proc Chem, 1 DNA Way, San Francisco, CA 94080 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2019年 / 141卷 / 41期

关键词：

BOND ACTIVATION; CHEMISTRY; INSERTION; ALKENES; CUT;

D O I：

10.1021/jacs.9b09344

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Herein we describe the development of a highly selective kinetic resolution of cyclobutanones via a Rh-catalyzed "cut-and-sew" reaction with selectivity factor up to 785. This reaction takes place at room temperature with excellent efficiency. Various trans-5,6-fused bicycles and C2-substituted cyclobutanones were obtained with excellent ee's that can be further used as chiral building blocks. DFT calculations reveal the crucial roles of the DTBM-segphos ligand in stabilizing the rate- and enantioselectivity-determining C-C oxidative addition transition state via favorable ligand substrate dispersion interactions.

引用

页码：16260 / 16265

页数：6

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