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Cobalt‐catalyzed enantio‐ and regioselective C(sp3)−H alkenylation of thioamides

Abstract:
An enantioselective cobalt-catalyzed C(sp3)−H alkenylation of thioamides with but-2-ynoate ester coupling partners employing thioamide directing groups is presented. The method is operationally simple and requires only mild reaction conditions, while providing alkenylated products as single regioisomers in excellent yields (up to 85 %) and high enantiomeric excess [up to 91 : 9 enantiomeric ratio (er), or up to >99 : 1 er after a single recrystallization]. Diverse downstream derivatizations of the products are demonstrated, delivering a range of enantioenriched constructs. Extensive computational studies using density functional theory provide insight into the detailed reaction mechanism, origin of enantiocontrol, and the unusual regioselectivity of the alkenylation reaction.
Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1002/ange.202316021

Authors


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
ORCID:
0000-0003-1512-9993


Publisher:
Wiley
Journal:
Angewandte Chemie More from this journal
Volume:
136
Issue:
13
Article number:
e202316021
Publication date:
2024-02-23
Acceptance date:
2023-12-20
DOI:
EISSN:
1521-3757
ISSN:
0044-8249


Language:
English
Keywords:
Pubs id:
1686553
Local pid:
pubs:1686553
Deposit date:
2024-03-10

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