Insight into the Mechanism of the Acylation of Alcohols with Acid Anhydrides Catalyzed by Phosphoric Acid Derivatives.
J Org Chem
; 86(7): 5197-5212, 2021 04 02.
Article
in En
| MEDLINE
| ID: mdl-33720717
ABSTRACT
Insight into the mechanism of a safe, simple, and inexpensive phosphoric acid (H3PO4)-catalyzed acylation of alcohols with acid anhydrides is described. The corresponding in situ-generated diacylated mixed anhydrides, unlike traditionally proposed monoacylated mixed anhydrides, are proposed as the active species. In particular, the diacylated mixed anhydrides act as efficient catalytic acyl transfer reagents rather than as Brønsted acid catalysts simply activating acid anhydrides. Remarkably, highly efficient phosphoric acid (1-3 mol %)-catalyzed acylation of alcohols with acid anhydrides was achieved and a 23 g scale synthesis of an ester was demonstrated. Also, phosphoric acid catalyst was effective for synthetically useful esterification from carboxylic acids, alcohols, and acid anhydride. Moreover, with regard to recent developments in chiral 1,1'-bi-2-naphthol (BINOL)-derived phosphoric acid diester catalysts toward asymmetric kinetic resolution of alcohols by acylation, some phosphate diesters were examined. As a result, a 31P NMR study and a kinetics study strongly supported not only the acid-base cooperative mechanism as previously proposed by other researchers but also the mixed anhydride mechanism as presently proposed by us.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
J Org Chem
Year:
2021
Document type:
Article
Affiliation country:
Japan