2:1 versus 1:1 Coupling of Alkylacetylenes with Secondary Amines: Selectivity Switching in 8-Quinolinolato Rhodium Catalysis
2:1 versus 1:1 Coupling of Alkylacetylenes with Secondary Amines: Selectivity Switching in 8-Quinolinolato Rhodium Catalysis
复制标题
烷基乙炔与仲胺的 2:1 与 1:1 偶联：8-喹啉铑催化中的选择性转换
DOI：
10.1021/acs.orglett.1c00094
复制
发表时间：
2021
期刊：
影响因子：
5.2
通讯作者：
F. Kakiuchi
中科院分区：
文献类型：
--
作者：
Y. Morimoto;M. Hamada;S. Takano;K. Mochizuki;T. Kochi;F. Kakiuchi
使用8-喹啉醇铑催化剂和CsF实现了烷基乙炔与仲胺的2:1和1:1偶联。通过选择反应溶剂来改变2:1/1:1的选择性。在DMA中，烷基乙炔与胺进行了前所未有的2:1偶联反应，得到了2-氨基二烯产品。一锅2:1偶联/还原可以快速获得各种烯丙胺，而一锅偶联/水解可以得到烯酮作为产物。甲苯在相对温和的条件下发生抗马尔可夫尼科夫氢胺化反应，得到1:1偶联产物。
Both 2:1 and 1:1 couplings of alkylacetylenes with secondary amines were achieved using 8-quinolinolato rhodium catalysts and CsF. The 2:1/1:1 selectivity was switched by choosing the reaction solvent. In DMA, an unprecedented 2:1 coupling reaction of alkylacetylenes with amines proceeded to give 2-aminodiene products. One-pot 2:1 coupling/reduction provided rapid access to various allylamines, while one-pot coupling/hydrolysis gave enones as products. In toluene, anti-Markovnikov hydroamination occurred under relatively mild conditions to give 1:1 coupling products.