Formal Addition of β‐Acylalkenyl Anions to Ketones Utilizing [1,2]‐Phospha‐Brook Rearrangement under Brønsted Base Catalysis

A methodology for the formal addition of β-acylalkenyl anions was developed by utilizing the [1,2]-phospha-Brook rearrangement under Brønsted base catalysis. The two-step reaction involves the catalytic addition of α-oxygenated propargyl anions generated via [1,2]-phospha-Brook rearrangement to electron-deficient ketones and subsequent alcoholysis to afford tertiary alcohols having an enone moiety. This is a rare example of a catalytic carbon-carbon bond forming reaction of β-acylalkenyl anion equivalents, providing synthetic building blocks that are otherwise difficult to access.