Open AccessKinetic Resolution via Rh-Catalyzed C–C Activation of Cyclobutanones at Room Temperature
Author(s) -
Lin Deng,
Yingjuan Fu,
Siu Yin Lee,
Chengpeng Wang,
Peng Liu,
Guangbin Dong
Publication year - 2019
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.9b09344
Subject(s) - chemistry , kinetic resolution , catalysis , ligand (biochemistry) , kinetic energy , selectivity , substrate (aquarium) , dispersion (optics) , transition state , oxidative addition , computational chemistry , photochemistry , stereochemistry , combinatorial chemistry , organic chemistry , enantioselective synthesis , receptor , biochemistry , physics , oceanography , quantum mechanics , geology , optics
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.