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 | |
| Publication status | Published - Oct 4 2002 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Organic Chemistry
Cite this
Platinum complex-catalyzed hydrosilylation and isomerization of methylenecyclopropane derivatives. Effect of structures of the substrate and catalyst. / Itazaki, Masumi; Nishihara, Yasushi; Osakada, Kohtaro.
In: Journal of Organic Chemistry, Vol. 67, No. 20, 04.10.2002, p. 6889-6895.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Platinum complex-catalyzed hydrosilylation and isomerization of methylenecyclopropane derivatives. Effect of structures of the substrate and catalyst
AU - Itazaki, Masumi
AU - Nishihara, Yasushi
AU - Osakada, Kohtaro
PY - 2002/10/4
Y1 - 2002/10/4
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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U2 - 10.1021/jo020293+
DO - 10.1021/jo020293+
M3 - Article
VL - 67
SP - 6889
EP - 6895
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 20
ER -