Reaction of Ti(NMe2)4 with allyl alcohols and primary amines leads to the selective formation of secondary allylic amines. The allyl transfer from the alcohol to the amine occurs with selective allylic transposition. Due to substituent effects in the reactions, we postulate that the reaction occurs through a [2 + 2]/retro-[2 + 2]-cycloaddition mechanism. It was also found that a similar reaction could
Ti(NMe2)4 与
烯丙醇和
伯胺的反应导致仲
烯丙胺的选择性形成。烯丙基从醇转移到胺发生选择性烯丙基转座。由于反应中的取代基效应,我们假设反应通过 [2 + 2]/逆-[2 + 2]-环加成机制发生。还发现用高
烯丙醇可以完成类似的反应。在这种情况下,更复杂的机制导致了 1-氮杂-螺[5.5]
十一烷的形成。讨论了同烯丙基转移和环化的可能途径。