Photoinduced Carboborative Ring Contraction Enables Regio- and Stereoselective Synthesis of Multiply Substituted Five-Membered Carbocycles and Heterocycles.

Abstract

We report herein a photoinduced carboborative ring contraction of monounsaturated six-membered carbocycles and heterocycles. The reaction produces substituted five-membered ring systems stereoselectively and on preparative scales. The products feature multiple stereocenters, including contiguous quaternary carbons. We show that the reaction can serve as a synthetic platform for ring system alteration of natural products. The reaction can also be used in natural product synthesis. A concise total synthesis of artalbic acid has been enabled by a sequence of photoinduced carboborative ring contraction, Rauhut-Currier reaction, and nitrilase-catalyzed hydrolysis. The synthetic utility of the reaction has been further demonstrated by converting the intermediate organoboranes to alcohols, amines, and alkenes.