
Chemistry - A European Journal p. 9250 - 9254 (2014)
Update date:2022-07-30
Topics:
Hermeke, Julia
Klare, Hendrik F. T.
Oestreich, Martin
A procedure for the synthesis of otherwise difficult-to-make N-silylated enamines, that is masked enamines derived from primary amines, is reported. The approach is based on formation of a silyliminium ion and subsequent abstraction of the acidified α-proton rather than α-deprotonation of the enolizable imine followed by reaction with an electrophilic silicon reagent. The silicon electrophile, stabilized by a sulfur atom, is generated by cooperative activation of an Si-H bond at the Ru-S bond of a tethered ruthenium(II) thiolate complex. After transfer of the silicon cation onto the imine nitrogen atom, the remaining ruthenium(II) hydride fulfills the role of the base. Deprotonation and release of dihydrogen close the catalytic cycle. The net reaction is a dehydrogenative Si-N coupling of enolizable imines and hydrosilanes. Silicon IN, hydrogen OUT: N-Silylated enamines are protected enamines derived from combinations of primary rather than secondary amines and enolizable carbonyl compounds. This rare class of compounds is now directly available from imines by a dehydrogenative Si-N coupling. The catalyst generates the silicon electrophile by Si-H bond activation and also acts as a base after transfer of the silicon electrophile onto the imine nitrogen atom (see scheme, Ar F=3,5-bis(trifluoromethyl)phenyl, Si=R3Si=triorganosilyl).
Shandong Yuanli Science and Technology Co., Ltd.
Contact:86-0536-6777557
Address:Zhuliu Industiral Park,Changle County
JIANGXI XINXIN CHEMICAL CO., LTD.
Contact:86-15957176628
Address:INDUSTRY ROAD 1, INDUSTRIAL PARK, HEKOU TOWN,YANSHAN COUNTY, JIANGXI PROVINCE, CHINA
Huzhou City Linghu Xinwang Chemical Co.,Ltd.
Contact:86-572-3948695/3945236
Address:huzhou
Shanghai Sharing technologies Co., Ltd.
Contact:86-021-66787223
Address:No11, Lane 225, Jinxiang Road,Pudong district
Contact:86-931-8272767
Address:Room 602, No.461, Nanchang Road, Chengguan District, Lanzhou City, China PRC
Doi:10.1016/S0040-4039(00)70173-0
(1966)Doi:10.1002/adsc.201300999
(2014)Doi:10.1039/c4ra01181c
(2014)Doi:10.1246/cl.1995.181
(1995)Doi:10.1080/15421406.2013.837996
(2014)Doi:10.1016/0040-4020(67)80035-8
(1967)