RESUMEN
Several alkylidenesilacyclopropanes were prepared by silver-mediated silylene transfer to allenes. Oxasilacyclopentanes derived from allenes were prepared with high regio- and diastereoselectivity by a two-step, one-flask silacyclopropanation/carbonyl insertion reaction. Triols and homoallylic alcohols were formed diastereoselectively by functionalizing the oxasilacyclopentanes. An optically active allene (>98% ee) was utilized to synthesize an enantiopure homoallylic alcohol in 96% ee.
Asunto(s)
Alcoholes/síntesis química , Alcadienos/química , Ciclopropanos/síntesis química , Silanos/síntesis química , Alcoholes/química , Catálisis , Técnicas Químicas Combinatorias , Ciclopropanos/química , Estructura Molecular , Silanos/química , EstereoisomerismoRESUMEN
Allylic ethers undergo insertions of silylenes into C-O bonds to form allylic silanes. Silylene insertion into C-O acetal bonds was also observed. Formation of silylene ylide intermediates led to [1,2]-Stevens rearrangement products as well as [2,3]-sigmatropic products depending upon the steric environment of the starting allylic ether.