Stereoselective 1,3-Insertions of Rhodium(II) Azavinyl Carbenes

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.