Platinum complex-catalyzed hydrosilylation and isomerization of methylenecyclopropane derivatives. Effect of structures of the substrate and catalyst

Masumi Itazaki; Yasushi Nishihara; Kohtaro Osakada

doi:10.1021/jo020293+

Platinum complex-catalyzed hydrosilylation and isomerization of methylenecyclopropane derivatives. Effect of structures of the substrate and catalyst

Masumi Itazaki, Yasushi Nishihara, Kohtaro Osakada

Research output: Contribution to journal › Article

61 Citations (Scopus)

Abstract

PtI₂(PPh₃)₂ catalyzes hydrosilylation of 2,2-diphenyl-1-methylenecyclopropane with HSiEt₃, HSiPh₃, HSiEt₂Ph, HSiPhCl₂, and HSiCl₃ under solvent-free conditions at 140°C to produce the silyl compounds with a (2,2-diphenylcyclopropyl)methyl substituent in moderate to high yields without ring-opening of the substrate. PtI₂(PPh₃)₂ is converted by the reaction into PtH(I)(PPh₃)₂, which also catalyzes the hydrosilylation of the methylenecyclopropanes. The reaction of 2-phenyl-1-methylenecyclopropane, 2-methyl-2-phenyl-1-methylenecyclopropane, 2,2-diphenethyl-1-methyl-enecyclopropane, and alkylidenecyclopropanes with HSiEt₃ catalyzed by PtI₂(PPh₃)₂ causes addition of hydrosilane to the substrate accompanied by ring-opening. 2,2-Diphenyl-1-methylenecyclopropane undergoes ring-opening isomerization in the presence of HSi(OEt)Me₂ and Pt(PEt₃)₃ catalyst to give 1,1-diphenyl-1,3-butadiene. The pathways for the hydrosilylation and the isomerization are discussed.

Original language	English
Pages (from-to)	6889-6895
Number of pages	7
Journal	Journal of Organic Chemistry
Volume	67
Issue number	20
DOIs	https://doi.org/10.1021/jo020293+
Publication status	Published - Oct 4 2002
Externally published	Yes

ASJC Scopus subject areas

Organic Chemistry

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Itazaki, M., Nishihara, Y., & Osakada, K. (2002). Platinum complex-catalyzed hydrosilylation and isomerization of methylenecyclopropane derivatives. Effect of structures of the substrate and catalyst. Journal of Organic Chemistry, 67(20), 6889-6895. https://doi.org/10.1021/jo020293+

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title = "Platinum complex-catalyzed hydrosilylation and isomerization of methylenecyclopropane derivatives. Effect of structures of the substrate and catalyst",

abstract = "PtI2(PPh3)2 catalyzes hydrosilylation of 2,2-diphenyl-1-methylenecyclopropane with HSiEt3, HSiPh3, HSiEt2Ph, HSiPhCl2, and HSiCl3 under solvent-free conditions at 140°C to produce the silyl compounds with a (2,2-diphenylcyclopropyl)methyl substituent in moderate to high yields without ring-opening of the substrate. PtI2(PPh3)2 is converted by the reaction into PtH(I)(PPh3)2, which also catalyzes the hydrosilylation of the methylenecyclopropanes. The reaction of 2-phenyl-1-methylenecyclopropane, 2-methyl-2-phenyl-1-methylenecyclopropane, 2,2-diphenethyl-1-methyl-enecyclopropane, and alkylidenecyclopropanes with HSiEt3 catalyzed by PtI2(PPh3)2 causes addition of hydrosilane to the substrate accompanied by ring-opening. 2,2-Diphenyl-1-methylenecyclopropane undergoes ring-opening isomerization in the presence of HSi(OEt)Me2 and Pt(PEt3)3 catalyst to give 1,1-diphenyl-1,3-butadiene. The pathways for the hydrosilylation and the isomerization are discussed.",

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PY - 2002/10/4

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N2 - PtI2(PPh3)2 catalyzes hydrosilylation of 2,2-diphenyl-1-methylenecyclopropane with HSiEt3, HSiPh3, HSiEt2Ph, HSiPhCl2, and HSiCl3 under solvent-free conditions at 140°C to produce the silyl compounds with a (2,2-diphenylcyclopropyl)methyl substituent in moderate to high yields without ring-opening of the substrate. PtI2(PPh3)2 is converted by the reaction into PtH(I)(PPh3)2, which also catalyzes the hydrosilylation of the methylenecyclopropanes. The reaction of 2-phenyl-1-methylenecyclopropane, 2-methyl-2-phenyl-1-methylenecyclopropane, 2,2-diphenethyl-1-methyl-enecyclopropane, and alkylidenecyclopropanes with HSiEt3 catalyzed by PtI2(PPh3)2 causes addition of hydrosilane to the substrate accompanied by ring-opening. 2,2-Diphenyl-1-methylenecyclopropane undergoes ring-opening isomerization in the presence of HSi(OEt)Me2 and Pt(PEt3)3 catalyst to give 1,1-diphenyl-1,3-butadiene. The pathways for the hydrosilylation and the isomerization are discussed.

AB - PtI2(PPh3)2 catalyzes hydrosilylation of 2,2-diphenyl-1-methylenecyclopropane with HSiEt3, HSiPh3, HSiEt2Ph, HSiPhCl2, and HSiCl3 under solvent-free conditions at 140°C to produce the silyl compounds with a (2,2-diphenylcyclopropyl)methyl substituent in moderate to high yields without ring-opening of the substrate. PtI2(PPh3)2 is converted by the reaction into PtH(I)(PPh3)2, which also catalyzes the hydrosilylation of the methylenecyclopropanes. The reaction of 2-phenyl-1-methylenecyclopropane, 2-methyl-2-phenyl-1-methylenecyclopropane, 2,2-diphenethyl-1-methyl-enecyclopropane, and alkylidenecyclopropanes with HSiEt3 catalyzed by PtI2(PPh3)2 causes addition of hydrosilane to the substrate accompanied by ring-opening. 2,2-Diphenyl-1-methylenecyclopropane undergoes ring-opening isomerization in the presence of HSi(OEt)Me2 and Pt(PEt3)3 catalyst to give 1,1-diphenyl-1,3-butadiene. The pathways for the hydrosilylation and the isomerization are discussed.

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