Hypervalent iodine(III) catalyzed radical hydroacylation of chiral alkylidenemalonates with aliphatic aldehydes under photolysis

Abstract

Hypervalent iodine(III) catalyzed diastereoselective radical hydroacylation of alkylidenemalonates bearing (−)-8-phenylmenthol as a chiral auxiliary with aliphatic aldehydes is realized under photolysis. This work represent the first example of diastereoselective addition of acyl radicals to olefins to afford chiral ketones in a highly stereoselective fashion. The reaction is initiated by the photolysis of hypervalent iodine(III) catalyst under mild and metal-free conditions. The synthetic potential of this methodology was demonstrated by the short formal synthesis of (−)-methyleneolactocin.