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

ABSTRACT: 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.

SUBMITTER: Deng L

PROVIDER: S-EPMC7075347 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature

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

Deng Lin L Fu Yue Y Lee Siu Yin SY Wang Chengpeng C Liu Peng P Dong Guangbin G

Journal of the American Chemical Society 20191002 41

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 <i>trans</i>-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- an ...[more]

PMID: 31568718

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