Control of Carbene Reactivity by Crystals. A Highly Selective 1,2-H Shift in the Solid-to-Solid Reaction of 1-(4'-Biphenylyl)-2-phenyldiazopropane to (Z)-1-(4'-Biphenylyl)-2-phenylpropene

摘要

Ruby red polycrystalline samples of 1-(4'-biphenylyl)-2-phenyldiazopropane (1a) efficiently transform into colorless (Z)-1-(4'-biphenylyl)-2-phenylpropene [(Z)-3a]in up to 96/100 yield in a highly selective photochemical solid-to-solid reaction. The solid state reaction was shown to proceed via a carbene intermediate, and it was formulated as a 1, 2-H shift with unprecedented stereoselectibity.