Decarboxylation of β-ketoesters in hexamethylphosphoric triamide

✍ Scribed by Paul Müller; Bernard Siegfried

• Publisher: Elsevier Science
• Year: 1973
• Tongue: French
• Weight: 209 KB
• Volume: 14
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)86971-9

✦ Synopsis

Ester cleavage by halide ions in dipolar aprotic solvents is believed to proceed by an SN2 process involving nucleophilic displacement of carboxylate ion from the alcohol (1,2,3). The synthetic methods making use of this reaction require elevated temperature (4), strong base (5) or air-sensitive reagents (6,7,8) which limits their general applicability.

Ester cleavage by nucleophilic attack on the alcohol is much more subjected to structural effects on the alcohol than is ester hydrolysis. Thus the reactivity of methylacetate is only 2.3 times