Modulating stereoselectivity in allylic C(sp3)-H bond arylations via nickel and photoredox catalysis.
Nat Commun
; 14(1): 548, 2023 Feb 01.
Article
em En
| MEDLINE
| ID: mdl-36725849
ABSTRACT
While significant progress has been made in developing selective C-H bond cross-couplings in the field of radical chemistry, the site and stereoselectivity remain a long-standing challenge. Here, we present the successful development of stereodivergent allylic C(sp3)-H bond arylations through a systematic investigation of the direction and degree of stereoselectivity in the cross-coupling process. In contrast to the signature photosensitized geometrical isomerization of alkenes, the catalytic reaction demonstrates the feasibility of switching the C-C double bond stereoselectivity by means of ligand control as well as steric and electronic effects. Computational studies explain the stereochemical outcome and indicate that excitation of a Ni-allyl complex from singlet to a triplet state results in a spontaneous change of the allyl group coordination and that the subsequent isomerization can be directed by the choice of the ligand to achieve E/Z selectivity.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Ano de publicação:
2023
Tipo de documento:
Article