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Dynamic kinetic resolution allows control of remote stereochemistry in asymmetric hydrogen borrowing alkylation

Abstract:
A catalytic asymmetric method for the synthesis of γ-substituted ketones via hydrogen borrowing alkylation of both racemic linear precursors and 1,5-diols is described. The base mediated racemization of an intermediate cyclohexenone to facilitates a dynamic kinetic resolution, affording highly enantioenriched cyclohexanes in excellent yields, which could be further functionalized by removal of the Ph* group. DFT modelling revealed the mode of enantioinduction to be a stepwise process comprising of a hydride transfer and a coordination change to a π-allylic enolate complex with the iridium catalyst.
Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1002/anie.202424959

Authors


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Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Role:
Author
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Role:
Author
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Role:
Author
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Role:
Author
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Role:
Author


More from this funder
Funder identifier:
https://ror.org/0439y7842
Grant:
EP/W02246X/1


Publisher:
Wiley
Journal:
Angewandte Chemie International Edition More from this journal
Volume:
64
Issue:
13
Article number:
e202424959
Publication date:
2025-02-27
Acceptance date:
2025-02-05
DOI:
EISSN:
1521-3773
ISSN:
1433-7851


Language:
English
Keywords:
Pubs id:
2083913
Local pid:
pubs:2083913
Deposit date:
2025-02-05

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