Hydride-Induced Novel Cyclization of Dienedinitriles Leading to Multifunctionalized Cyclopentadienes

By treatment with LiAlH4, 1,4-dicyano-1,4-bis(trimethylsilyl)-1,3-dienes underwent a novel hydride-induced nucleophilic intermolecular 1,4-addition to the α,β-unsaturated nitrile moiety, followed by an immediate nucleophilic intramolecular 1,2-addition to the remaining CN group, to afford multiply functionalized cyclopentadienes in high isolated yields. These multifunctional (−CN, −NH2, −SiMe3, −H) cyclopentadienes are of a rich and interesting reaction chemistry as preliminarily demonstrated by their reaction with ArNCO involving both the substituent and the ring.

通过氢化铝锂（LiAlH4）处理，1,4-二氰基-1,4-双(三甲基硅基)-1,3-二烯烃发生了一种新型的氢化物诱导亲核分子间1,4-加成反应，作用于α,β-不饱和腈基团，随后立即对剩余氰基发生亲核分子内1,2-加成反应，最终以高分离产率得到多官能团化环戊二烯。这类带有(-CN、-NH2、-SiMe3、-H)多官能团的环戊二烯具有丰富且有趣的反应化学特性，初步研究表明，它们可与芳基异氰酸酯（ArNCO）发生涉及取代基与环本身的反应。