Development of Synthetic Procedure of Allylamines via Oxidative Cyclization on Nickel and Unique Nickel/Aluminum Transmetalation

通过镍催化的炔、亚胺和AlMe 3的三组分环缩合反应，合成了一种新型的氮杂铝环戊烯，它是合成γ-取代烯丙基胺的前体.在该反应中，由炔和亚胺氧化环化生成的氮杂镍杂环是关键中间体。另一方面，以Me_2AlOTf为添加剂，使醛和炔与镍（0）发生氧化环化反应，生成氧杂镍环戊烯，再与AlMe_3反应生成相应的氧杂铝环戊烯。

Aza-aluminacyclopentenes, which serve a useful precursor for γ-substituted allylamines, were catalytically prepared from novel Ni-mediated three-component cyclocondensation reaction of an alkyne, an imine, and AlMe3. In this reaction, azanickelacycle generated by the oxidative cyclization of an alkyne and an imine is a key intermediate. On the other hand, the use of Me_2AlOTf as an additive allowed the oxidative cyclization of an aldehyde and an alkyne with nickel(0) to give an oxanickelacyclopentene, treatment of which with AlMe_3 yielded the corresponding oxaaluminacyclopentene.