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Directing the Stereoselectivity of the Claisen Rearrangement to Form Cyclic Ketones with Full Substitution at the α-Positions.

Authors :
Badmus FO
Thombal RS
Philkhana SC
Malone JA
Bailey CE
Armendariz-Gonzalez E
Mureka EW
Locicero CM
Fronczek FR
Kartika R
Source :
Organic letters [Org Lett] 2023 Oct 27; Vol. 25 (42), pp. 7622-7627. Date of Electronic Publication: 2023 Oct 13.
Publication Year :
2023

Abstract

We report an enantioselective synthesis of cyclic ketones with full substitutions at the α-positions in a highly diastereoselective manner. Our method is achieved by subjecting substrate motifs in 2-allyloxyenones to chiral organomagnesium reagents, which trigger the Claisen rearrangement upon direct 1,2-carbonyl addition. The observed diastereoselectivity of the allyl migration is proposed to originate from the intramolecular chelation of the magnesium alkoxide to the allyloxy moiety.

Details

Language :
English
ISSN :
1523-7052
Volume :
25
Issue :
42
Database :
MEDLINE
Journal :
Organic letters
Publication Type :
Academic Journal
Accession number :
37830497
Full Text :
https://doi.org/10.1021/acs.orglett.3c02752