Department of Chemistry, Zhejiang University, Hangzhou 310027, People's Republic of China.
J Org Chem. 2010 Jul 2;75(13):4554-61. doi: 10.1021/jo1007898.
The cross coupling of the C-OMe bond adjacent to a nitrogen atom in dialkoxy-N,N-dialkylmethanamines with terminal alkynes was efficiently approached in the presence of copper catalyst under mild conditions to give 3-amino-1,4-diynes in good yields. The reaction is promoted by phosphine ligands and the chemistry provides a simple and efficient route to 3-amino-1,4-diynes. Importantly, the Michael addition occurred with as-prepared 3-amino-1,4-diynes to give the useful Michael-adducts containing tert-alkylamines in a very convenient way. Further studies revealed that (E)-1,5-diarylpent-1-en-4-yn-3-one was formed through the rearrangement by using the neutral alumina column, and the corresponding imine 2-(1,5-diphenylpent-2-en-4-ynylideneamino)ethanol was obtained in the presence of AgOTf.
氮原子邻位的 C-OMe 键与二烷氧基-N,N-二烷基甲胺的末端炔烃的交叉偶联在温和条件下在铜催化剂的存在下高效进行，以高收率得到 3-氨基-1,4-二炔。该反应受膦配体的促进，该化学提供了一种简单有效的方法来制备 3-氨基-1,4-二炔。重要的是，迈克尔加成反应发生在新制备的 3-氨基-1,4-二炔上，非常方便地得到了含有叔烷基胺的有用的迈克尔加成产物。进一步的研究表明，（E）-1,5-二芳基戊-1-烯-4-炔-3-酮通过使用中性氧化铝柱进行重排而形成，并且在 AgOTf 的存在下得到相应的亚胺 2-（1,5-二苯基戊-2-烯-4-炔基氨基）乙醇。
