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An Unprecedented (Semi)Favorskii Rearrangement. Evidence for the 2-(Acyloxy)cyclopropanones
Santu Sadhukhan1, Beeraiah Baire1
1Department of Chemistry , Indian Institute of Technology Madras , Chennai , Tamilnadu 600036 , India.
Abstract:
Discovery and development of an unprecedented (semi)Favorskii rearrangement has been reported. The intermediacy of structurally singular (acyloxy)cyclopropanones has been unraveled by fruitful control experiments including a crossover experiment. This class of cyclopropanones is found to be inert for classical Favorskii functionalization and preferably undergoes a decycloisomerization (ring-chain valence tautomerism) to α-(acyloxy)enones. A cascade conversion of α,α-diiodo-α'-acetoxyketones to (acyloxy)cyclopropanones via α-iodo-α'-acetoxyketones has been achieved by the synchronous dual basicity (Lewis and Brønsted) of amines. The overall process is found to be very general for diverse substrates and highly efficient.
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