Bicyclopropylidene. A unique tetrasubstituted alkene and versatile C-6-building block for organic synthesis

Abstract

Bicyclopropylidene (4), now readily available in preparatively viable quantities, is evolving as a useful C-6 building block for organic synthesis due to its enhanced reactivity at the C-H, the C=C, as well as both types of C-C single bonds. Monosubstituted derivatives are accessible by deprotonation/electrophilic substitution. Di- and tetrasubstituted bicyclopropylidenes are best made by copper-mediated reductive dimerization of bromolithiocarbenoids. The 1,3-dipolar cycloadducts of nitrones rearrange to spirocyclopropanated piperidones, palladium-catalyzed codimerizations with acrylates occur with opening of one of the rings to yield precursors to bicyclo[3.3.0]octene and bicyclo[5.3.0]decene skeletons. Silicon-heteroatom bonds can be added across the double bond of 4 under palladium catalysis just like across a C=C triple bond, and carbopalladation of the double bond in 4 occurs more rapidly than that in an acrylate. A variety of new three-component reactions of 4 with alkenyl as well as aryl halides and dienophiles have been developed and extended to be carried out in a combinatorial sense, even on a polymer support, with an additional dimension added in the cleavage step. Most of the reported reactions of bicyclopropylidene (4) proceed with good to excellent yields.