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A vinyl cyclopropane ring expansion and iridium‐catalyzed hydrogen borrowing cascade

Abstract:
A vinyl cyclopropane rearrangement embedded in an iridium‐catalyzed hydrogen borrowing reaction enabled the formation of substituted stereo‐defined cyclopentanes from Ph* methyl ketone and cyclopropyl alcohols. Mechanistic studies provide evidence for the ring‐expansion reaction being the result of a cascade based on oxidation of the cyclopropyl alcohols, followed by aldol condensation with the pentamethyl phenyl‐substituted ketone to form an enone containing the vinyl cyclopropane. Subsequent single electron transfer (SET) to this system initiates a rearrangement, and the catalytic cycle is completed by reduction of the new enone. This process allows for the efficient formation of diversely substituted cyclopentanes as well as the construction of complex bicyclic carbon skeletons containing up to four contiguous stereocentres, all with high diastereoselectivity.
Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1002/ange.202003614

Authors


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Division:
MPLS
Department:
Chemistry
Role:
Author


Publisher:
Wiley
Journal:
Angewandte Chemie More from this journal
Volume:
132
Issue:
28
Pages:
11435-11440
Publication date:
2020-05-07
Acceptance date:
2020-04-21
DOI:
EISSN:
1521-3757
ISSN:
0044-8249


Language:
English
Keywords:
Pubs id:
1100934
Local pid:
pubs:1100934
Deposit date:
2020-04-22

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