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Title: Rhodium‐Catalyzed Enantioselective Silylation of Cyclopropyl C−H Bonds
Abstract

Hydrosilyl ethers, generated in situ by the dehydrogenative silylation of cyclopropylmethanols with diethylsilane, undergo asymmetric, intramolecular silylation of cyclopropyl C−H bonds in high yields and with high enantiomeric excesses in the presence of a rhodium catalyst derived from a rhodium precursor and the bisphosphine (S)‐DTBM‐SEGPHOS. The resulting enantioenriched oxasilolanes are suitable substrates for the Tamao–Fleming oxidation to form cyclopropanols with conservation of theeevalue from the C−H silylation. Preliminary mechanistic data suggest that C−H cleavage is likely to be the turnover‐limiting and enantioselectivity‐determining step.

 
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PAR ID:
10236132
Author(s) / Creator(s):
 ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Angewandte Chemie
Volume:
128
Issue:
30
ISSN:
0044-8249
Page Range / eLocation ID:
p. 8865-8869
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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