Enantioselective Double Carbonylation Enabled by High-Valent Palladium Catalysis.
J Am Chem Soc
; 144(47): 21800-21807, 2022 11 30.
Article
in En
| MEDLINE
| ID: mdl-36383694
ABSTRACT
Palladium-catalyzed carbonylation reactions are efficient methods for synthesizing valuable molecules. However, realizing a carbonylation with excellent yield and chemo-, regio-, and enantioselectivities by classical low-valent palladium catalysis is highly challenging. Herein, we describe an enantioselective carbonylation reaction using a high-valent palladium catalysis strategy and employing a chiral sulfoxide phosphine (SOP) ligand. This double aminocarbonylation reaction begins with the formation of a carbamoylpalladium(II) species, which undergoes enantioselective oxidative addition with a cyclic diaryliodonium salt to generate a palladium(IV) intermediate, followed by a second CO insertion and reductive elimination. The mechanism has been illustrated with experimental and computational studies.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Main subject:
Palladium
/
Sulfoxides
Language:
En
Journal:
J Am Chem Soc
Year:
2022
Document type:
Article
Affiliation country:
China