Geometrically Compelled Silicon(II)/Silicon(IV) Donor-Acceptor Interaction Enables the Enamination of Nitriles.
Angew Chem Int Ed Engl
; 62(49): e202315249, 2023 Dec 04.
Article
em En
| MEDLINE
| ID: mdl-37877345
ABSTRACT
Discovering new bonding scenarios and subsequently exploring the reactivity contribute substantially to advance the main group element chemistry. Herein, we report on the isolation and characterization of an intriguing class of the hydrido-benzosiloles 2-4. These compounds exhibit a side arm of the amidinatosilylenyl group, featuring unidirectional silicon(II)/silicon(IV) donor-acceptor interaction on account of the geometric constraint. Furthermore, the reactions involving 2-4 with nitriles yield the tricyclic compounds that edge-fused of the Si-heteroimidazolidine-CN2 Si2 , silole-C4 Si, and phenyl-C6 -rings (5-13). These compounds are manifesting a unique reaction that the silicon(II)/silicon(IV) interaction enables the enamination of the α-H-bearing nitriles. The reaction mechanism involved in H-shift under oxidative addition at silylene followed by hydrosilylation of a ketenimine intermediate was revealed by density function theory (DFT) calculations.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Ano de publicação:
2023
Tipo de documento:
Article
País de afiliação:
China