1311202-75-1Relevant academic research and scientific papers
Synthesis of α-silylmethyl-α,β-unsaturated imines by the rhodium-catalyzed silylimination of primary-alkyl-substituted terminal alkynes
Fukumoto, Yoshiya,Shimizu, Hiroto,Tashiro, Aya,Chatani, Naoto
, p. 8221 - 8227 (2014)
In contrast to our previous report on the rhodium-catalyzed reaction of terminal alkynes with equimolar amounts of hydrosilanes and isocyanides leading to (E)- or (Z)-β-silyl-α,β-unsaturated imines A, the addition of an excess molar amount of hydrosilanes relative to isocyanides in the reaction of primary-alkyl-substituted terminal alkynes results in the production of α-silylmethyl-α,β-unsaturated imines B. Various isocyanides bearing tert-butyl and 1-adamantyl groups gave B with good product selectivity. Z isomers were formed stereoselectively in many cases. Regarding the mechanism for this reaction, when the hydrosilane was added to the reaction mixture in two portions, unsaturated imines A were initially formed, which then underwent double-bond isomerization, probably catalyzed by a Rh-H species, to give B.
Switch in stereoselectivity caused by the isocyanide structure in the rhodium-catalyzed silylimination of alkynes
Fukumoto, Yoshiya,Hagihara, Motoyuki,Kinashi, Fuyuko,Chatani, Naoto
supporting information; experimental part, p. 10014 - 10017 (2011/08/22)
The reaction of terminal alkynes with hydrosilanes and tert-alkyl isocyanides in the presence of Rh4(CO)12 gives (Z)-β-silyl-α,β-unsaturated imines in good yields. On the other hand, the use of aryl isocyanides in place of tert-alkyl isocyanides leads to the formation of E isomers.
