Stereoselective 1,3-insertions of rhodium(II) azavinyl carbenes
Stepan Chuprakov1, Brady T Worrell, Nicklas Selander
1Department of Chemistry, The Scripps Research Institute , 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
Abstract:
Rhodium(II) azavinyl carbenes, conveniently generated from 1-sulfonyl-1,2,3-triazoles, undergo a facile, mild, and convergent formal 1,3-insertion into N-H and O-H bonds of primary and secondary amides, various alcohols, and carboxylic acids to afford a wide range of vicinally bisfunctionalized (Z)-olefins with perfect regio- and stereoselectivity. Utilizing the distinctive functionality installed through these reactions, a number of subsequent rearrangements and cyclizations expand the repertoire of valuable organic building blocks constructed by reactions of transition-metal carbene complexes, including α-allenyl ketones and amino-substituted heterocycles.
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