Combined Computational and Experimental Study Reveals Complex Mechanistic Landscape of Brønsted Acid-Catalyzed Silane-Dependent PâO Reduction.
J Am Chem Soc
; 146(20): 13983-13999, 2024 May 22.
Article
em En
| MEDLINE
| ID: mdl-38736283
ABSTRACT
The reaction mechanism of Brønsted acid-catalyzed silane-dependent PâO reduction has been elucidated through combined computational and experimental methods. Due to its remarkable chemo- and stereoselective nature, the Brønsted acid/silane reduction system has been widely employed in organophosphine-catalyzed transformations involving P(V)/P(III) redox cycle. However, the full mechanistic profile of this type of PâO reduction has yet to be clearly established to date. Supported by both DFT and experimental studies, our research reveals that the reaction likely proceeds through mechanisms other than the widely accepted "dual activation mode by silyl ester" or "acid-mediated direct PâO activation" mechanism. We propose that although the reduction mechanisms may vary with the substitution patterns of silane species, Brønsted acid generally activates the silane rather than the PâO group in transition structures. The proposed activation mode differs significantly from that associated with traditional Brønsted acid-catalyzed CâO reduction. The uniqueness of PâO reduction originates from the dominant Si/OâP orbital interactions in transition structures rather than the P/H-Si interactions. The comprehensive mechanistic landscape provided by us will serve as a guidance for the rational design and development of more efficient PâO reduction systems as well as novel organophosphine-catalyzed reactions involving P(V)/P(III) redox cycle.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
J Am Chem Soc
Ano de publicação:
2024
Tipo de documento:
Article
País de afiliação:
China
País de publicação:
Estados Unidos