Metal-catalyzed hydrosilylation of alkenes and alkynes using dimethyl(pyridyl)silane

Kenichiro Itami, Koichi Mitsudo, Akira Nishino, Jun Ichi Yoshida

Research output: Contribution to journalArticle

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Abstract

Metal-catalyzed hydrosilylation of alkenes and alkynes using dimethyl(pyridyl)silane is described. The hydrosilylation of alkenes using dimethyl(2-pyridyl)silane (2-PyMe2SiH) proceeded well in the presence of a catalytic amount of RhCl(PPh3)3 with virtually complete regioselectivity. By taking advantage of the phase tag property of the 2-PyMe2Si group, hydrosilylation products were isolated in greater than 95% purity by simple acid-base extraction. Strategic catalyst recovery was also demonstrated. The hydrosilylation of alkynes using 2-PyMe2SiH proceeded with a Pt(CH2= CHSiMe2)2O/P(t-Bu)3 catalyst to give alkenyldimethyl(2-pyridyl)silanes in good yield with high regioselectivity. A reactivity comparison of 2-PyMe2SiH with other related hydrosilanes (3-PyMe2SiH, 4-PyMe2SiH, and PhMe2SiH) was also performed. In the rhodium-catalyzed reaction, the reactivity order of hydrosilane was 2-PyMe2SiH ≫ 3-PyMe2SiH, 4-PyMe2SiH, PhMe2SiH, indicating a huge rate acceleration with 2-PyMe2SiH. In the platinum-catalyzed reaction, the reactivity order of hydrosilane was PhMe2SiH, 3-PyMe2SiH ≫ 4-PyMe2SiH > 2-PyMe2SiH, indicating a rate deceleration with 2-PyMe2SiH and 4-PyMe2SiH. It seems that these reactivity differences stem primarily from the governance of two different mechanisms (Chalk-Harrod and modified ChalkHarrod mechanisms). From the observed reactivity order, coordination and electronic effects of dimethyl(pyridyl)silanes have been implicated.

Original languageEnglish
Pages (from-to)2645-2652
Number of pages8
JournalJournal of Organic Chemistry
Volume67
Issue number8
DOIs
Publication statusPublished - Apr 19 2002
Externally publishedYes

Fingerprint

Hydrosilylation
Silanes
Alkynes
Alkenes
Metals
Regioselectivity
Rhodium
Catalysts
Calcium Carbonate
Deceleration
Platinum
Recovery
Acids

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Metal-catalyzed hydrosilylation of alkenes and alkynes using dimethyl(pyridyl)silane. / Itami, Kenichiro; Mitsudo, Koichi; Nishino, Akira; Yoshida, Jun Ichi.

In: Journal of Organic Chemistry, Vol. 67, No. 8, 19.04.2002, p. 2645-2652.

Research output: Contribution to journalArticle

Itami, Kenichiro ; Mitsudo, Koichi ; Nishino, Akira ; Yoshida, Jun Ichi. / Metal-catalyzed hydrosilylation of alkenes and alkynes using dimethyl(pyridyl)silane. In: Journal of Organic Chemistry. 2002 ; Vol. 67, No. 8. pp. 2645-2652.
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abstract = "Metal-catalyzed hydrosilylation of alkenes and alkynes using dimethyl(pyridyl)silane is described. The hydrosilylation of alkenes using dimethyl(2-pyridyl)silane (2-PyMe2SiH) proceeded well in the presence of a catalytic amount of RhCl(PPh3)3 with virtually complete regioselectivity. By taking advantage of the phase tag property of the 2-PyMe2Si group, hydrosilylation products were isolated in greater than 95{\%} purity by simple acid-base extraction. Strategic catalyst recovery was also demonstrated. The hydrosilylation of alkynes using 2-PyMe2SiH proceeded with a Pt(CH2= CHSiMe2)2O/P(t-Bu)3 catalyst to give alkenyldimethyl(2-pyridyl)silanes in good yield with high regioselectivity. A reactivity comparison of 2-PyMe2SiH with other related hydrosilanes (3-PyMe2SiH, 4-PyMe2SiH, and PhMe2SiH) was also performed. In the rhodium-catalyzed reaction, the reactivity order of hydrosilane was 2-PyMe2SiH ≫ 3-PyMe2SiH, 4-PyMe2SiH, PhMe2SiH, indicating a huge rate acceleration with 2-PyMe2SiH. In the platinum-catalyzed reaction, the reactivity order of hydrosilane was PhMe2SiH, 3-PyMe2SiH ≫ 4-PyMe2SiH > 2-PyMe2SiH, indicating a rate deceleration with 2-PyMe2SiH and 4-PyMe2SiH. It seems that these reactivity differences stem primarily from the governance of two different mechanisms (Chalk-Harrod and modified ChalkHarrod mechanisms). From the observed reactivity order, coordination and electronic effects of dimethyl(pyridyl)silanes have been implicated.",
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AB - Metal-catalyzed hydrosilylation of alkenes and alkynes using dimethyl(pyridyl)silane is described. The hydrosilylation of alkenes using dimethyl(2-pyridyl)silane (2-PyMe2SiH) proceeded well in the presence of a catalytic amount of RhCl(PPh3)3 with virtually complete regioselectivity. By taking advantage of the phase tag property of the 2-PyMe2Si group, hydrosilylation products were isolated in greater than 95% purity by simple acid-base extraction. Strategic catalyst recovery was also demonstrated. The hydrosilylation of alkynes using 2-PyMe2SiH proceeded with a Pt(CH2= CHSiMe2)2O/P(t-Bu)3 catalyst to give alkenyldimethyl(2-pyridyl)silanes in good yield with high regioselectivity. A reactivity comparison of 2-PyMe2SiH with other related hydrosilanes (3-PyMe2SiH, 4-PyMe2SiH, and PhMe2SiH) was also performed. In the rhodium-catalyzed reaction, the reactivity order of hydrosilane was 2-PyMe2SiH ≫ 3-PyMe2SiH, 4-PyMe2SiH, PhMe2SiH, indicating a huge rate acceleration with 2-PyMe2SiH. In the platinum-catalyzed reaction, the reactivity order of hydrosilane was PhMe2SiH, 3-PyMe2SiH ≫ 4-PyMe2SiH > 2-PyMe2SiH, indicating a rate deceleration with 2-PyMe2SiH and 4-PyMe2SiH. It seems that these reactivity differences stem primarily from the governance of two different mechanisms (Chalk-Harrod and modified ChalkHarrod mechanisms). From the observed reactivity order, coordination and electronic effects of dimethyl(pyridyl)silanes have been implicated.

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