| Abstract
| - A 1:1 mixture of the platinum dimethyl diimine complex [PhNC(Me)C(Me)NPh]PtMe2 (4a) andB(C6F5)3 catalyzed the cyclization/hydrosilylation of dimethyl dipropargylmalonate (1) and HSiEt3to form 1,1-dicarbomethoxy-3-methylene-4-(triethylsilylmethylene)cyclopentane (3) in 82% isolatedyield with 26:1 Z:E selectivity. Platinum-catalyzed diyne cyclization/hydrosilylation tolerated a rangeof functional groups including esters, sulfones, acetals, silyl ethers, amides, and hindered ketones.Diynes that possessed propargylic substitution underwent facile cyclization/hydrosilylation to formsilylated 1,2-dialkylidene cyclopentanes as mixtures of regioisomers. Diynes that possessed anelectron-deficient internal alkyne underwent cyclization/hydrosilylation in moderate yield to formproducts resulting from silyl transfer to the less substituted alkyne. The silylated 1,2-dialkylidenecyclopentanes formed via diyne cyclization/hydrosilylation underwent a range of transformations including protodesilylation, Z/E isomerization, and [4 + 2] cycloaddition with dieneophiles.
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