144776-78-3Relevant articles and documents
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 (2015/03/18)
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.
Rhodium catalyzed transformation of propargylamines to 2-silylmethyl-2-alkenals: Formal silylformylation of allenes
Matsuda,Sakakibara,Inoue,Nagashima
, p. 5799 - 5802 (2007/10/02)
Propargylamines are effectively transformed to 2-dimethylphenylsilylmethyl-2-alkenals by the interaction of two equivalents of Me2PhSiH under silylformylation conditions catalyzed by Rh4(CO)12. The products are not obtained directly by silylformylation of the corresponding allenes.
