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. 2017 Aug 23;139(33):11365-11368.
doi: 10.1021/jacs.7b07128. Epub 2017 Aug 9.

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

Shengfei Jin  1 , Vu T Nguyen  1 , Hang T Dang  1 , Dat P Nguyen  1 , Hadi D Arman  1 , Oleg V Larionov  1
Affiliations

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

Shengfei Jin et al. J Am Chem Soc. .

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.

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Figures

Scheme 1
Scheme 1. Photoinduced Carboborative Ring Contraction
Scheme 2
Scheme 2. Synthesis of Artalbic Acid
Scheme 3
Scheme 3. Structural Diversification of the Carboborative Ring Contraction Products
See this image and copyright information in PMC

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