Ni(II)-catalyzed asymmetric alkenylations of ketimines

• DOI: 10.1038/s41467-018-04645-3
• Publication Date: 2018-06-04T16:01:20Z
• Authors: Mao Quan; Xiaoxiao Wang; Liang Wu; Ilya D. Gridnev; Guoqiang Yang; Wanbin Zhang
• Keywords: Stereospecificity

Chiral allylic amines are not only present in many bioactive compounds, but can also be readily transformed to other chiral amines. Therefore, the asymmetric synthesis of is highly desired. Herein, we report two types Ni(II)-catalyzed alkenylation cyclic ketimines for preparation When bear alkyl or alkoxycarbonyl groups, gives five- and six-membered α-tertiary amine products with excellent yields enantioselectivities under mild reaction conditions. A variety used method tolerates some variation alkenylboronic acid scope. Furthermore, alkenyl five-membered ketimine substrates, an alkenylation/rearrangement occurs, providing seven-membered sulfamide bearing a conjugated diene skeleton enantioselectivities. Mechanistic studies reveal that ring expansion step stereospecific site-selective process, which catalyzed by (Lewis Brønsted acid).