Preparation of 2-Alkenylsilanes and 2-Alkenylstannanes by the Reaction of 2-Alkenyl-1,1-cyclopropanedicarboxylate Esters with PhMe2SiAlEt2 and (Ph3Sn)2Zn. Generation of 2-Alkenyl-3-cyclopentene-1,1-dicarboxylates via Alkenyl Substituted π-Allylpalladium Complexes Derived from Dienylsilanes and [PdCl2(CH3CN)2]

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Abstract
Reaction of 2-vinyl-1,1-cyclopropanedicarboxylate with PhMe2SiAlEt2, PhMe2SiZnEt2Li, or (Ph3Sn)2Zn gave 1,7-homoconjugate addition products, 2-alkenylsilanes or 2-alkenylstannanes. In a similar fashion, 2-(1,3-butadienyl)-1,1-cyclopropanedicarboxylate provided the corresponding 1,9-homoconjugate adducts, dienylsilanes or dienylstannanes. The adducts were converted into π-allylpalladium complexes by means of [PdCl2(CH3CN)2]. Treatment of the alkenyl-substituted π-allylpalladium complexes derived from dienylsilanes and [PdCl2(CH3CN)2] with bases such as PPh3 or Na2CO3 gave 2-alkenyl-3-cyclopentene-1,1-dicarboxylates. In contrast, the reaction of the π-allylpalladiums generated from 2-alkenylsilanes and [PdCl2(CH3CN)2] with the bases resulted in the formation of original vinylcyclopropane derivatives.