Palladium-Catalyzed Allylation of Endocyclic 1-Azaallyl Anions.
J Org Chem
; 89(12): 8896-8905, 2024 Jun 21.
Article
in En
| MEDLINE
| ID: mdl-38856706
ABSTRACT
Endocyclic 1-azaallyl anions engage allyl acetates in a palladium-catalyzed allylation followed by reduction to give unprotected 2-(hetero)aryl-3-allylpiperidines and 2-allyl-3-arylmorpholines, products not easily accessible by other means. The allyl group is then readily transformed into a variety of functional groups. Preliminary studies on the asymmetric variant of the reaction using an enantiomerically pure BI-DIME-type ligand provide the product with moderate enantioselectivity. Computational studies suggest that energy barriers of inner-sphere reductive elimination and outer-sphere nucleophilic substitution are almost the same, which makes both of them possible reaction pathways. In addition, the inner-sphere mechanism displays an enantiodiscriminating C-C bond forming step, while the outer-sphere mechanism is much less selective, which combined to give the asymmetric variant of the reaction moderate enantioselectivity.
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Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
J Org Chem
Year:
2024
Document type:
Article