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Hydrogen borrowing catalysis with secondary alcohols: a new route for the generation of β-branched carbonyl compounds

Abstract:
A hydrogen borrowing reaction employing secondary alcohols and Ph* (Me5C6) ketones to give β-branched carbonyl products is described (21 examples). This new C-C bond forming process requires low loadings of [Cp*IrCl2]2, relatively low temperatures, and up to 2.0 equiv of the secondary alcohol. Substrate-induced diastereoselectivity was observed, and this represents the first example of a diastereoselective enolate hydrogen borrowing alkylation. By utilizing the Ph* group, the β-branched products could be straightforwardly cleaved to the corresponding esters or amides using a retro-Friedel-Crafts reaction. Finally, this protocol was applied to the synthesis of fragrance compound (±)-3-methyl-5-phenylpentanol.
Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1021/jacs.6b12840

Authors


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


More from this funder
Funding agency for:
Frost, J
Donohoe, T
Grant:
EP/L023121/1
EP/L023121/1
More from this funder
Funding agency for:
Cheong, C
More from this funder
Funding agency for:
Akhtar, W


Publisher:
American Chemical Society
Journal:
Journal of the American Chemical Society More from this journal
Volume:
139
Issue:
7
Pages:
2577–2580
Publication date:
2017-02-08
Acceptance date:
2017-02-01
DOI:
ISSN:
1520-5126


Language:
English
Pubs id:
pubs:679457
UUID:
uuid:d662c142-50bb-442d-babf-68d13afb60c4
Local pid:
pubs:679457
Source identifiers:
679457
Deposit date:
2017-02-22

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