Carbene-Catalyzed Tandem [1,2]-Phospha-Brook/[1,4]-Phosphate Rearrangement: Access to α-Ketophosphates via Controlled Cross-Acyloin Condensation.

The first N-heterocyclic carbene (NHC)-organocatalytic tandem [1,2]-phospha-Brook/[1,4]-phosphate rearrangement is reported. Acyl phosphonates, unlike acyl silanes that are well-exploited, make entry as the acyl anion precursors under NHC catalysis. The reactions proceed with absolute chemoselectivity via cross-acyloin condensation between acyl phosphonates and aldehydes giving the products α-ketophosphates in good to excellent yields. The challenging (enolizable) aliphatic-aliphatic substrates coupling also furnished the desired product in a good yield.