Stereodivergent Syntheses of (Z)- and (E)-Alkenylsilanes via Hydrosilylation of Terminal Alkynes Catalyzed by Rhodium(I) Iodide Complexes and Application to Silicon-Containing Polymer Syntheses

Atsunori Mori, Eisuke Takahisa, Yuichi Yamamura, Tsuyoshi Kato, Anoma P. Mudalige, Hiroshi Kajiro, Kazunori Hirabayashi, Yasushi Nishihara, Tamejiro Hiyama

Research output: Contribution to journalArticle

81 Citations (Scopus)

Abstract

RhI(PPh3)3 or [RhI(cod)]2 (cod = 1,5-cyclooctadiene) as a catalyst delivers both (Z)- and (E)-alkenylsilanes in the stereodivergent hydrosilylation of terminal alkynes with heteroatom-substituted organosilane reagents. Treatment of the rhodium catalyst and the silane reagent followed by addition of terminal alkyne at room temperature leads to (Z)-silanes, while addition of the silane and the alkyne to the rhodium catalyst in one portion and heating at 60°C affords (E)-silanes highly selectively. The obtained (E)- and (Z)-alkenylsilanes bearing heteroatom substituents on the silicon atom are subjected to the palladium-catalyzed cross-coupling reaction with aryl halides to form a carbon-carbon bond with retention of stereochemistry. The stereodivergent hydrosilylations are applied to the polyaddition with bifunctional alkynes (1,3- and 1,4-diethynylbenzene) and silanes (1,3- or 1,4-bis(dimethylsilyl)benzene), giving silicon-containing polymers, poly(aryleneethenylenesilylene)s, in highly stereocontrolled manners. A fluorine-containing silicon reagent bearing a 3,3,3-trifluoropropyl group is also subjected to the polymerization, in which [Rhl(cod)]2 is found to be an efficient catalyst. Measurement of UV-vis absorption/emission spectra and several thermal analyses of the polymers are also conducted.

Original languageEnglish
Pages (from-to)1755-1765
Number of pages11
JournalOrganometallics
Volume23
Issue number8
DOIs
Publication statusPublished - Apr 12 2004
Externally publishedYes

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silicon polymers
Hydrosilylation
Silanes
Rhodium
Alkynes
Iodides
alkynes
Silicon
rhodium
silanes
iodides
Polymers
Bearings (structural)
reagents
synthesis
catalysts
Catalysts
Carbon
Stereochemistry
Fluorine

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Stereodivergent Syntheses of (Z)- and (E)-Alkenylsilanes via Hydrosilylation of Terminal Alkynes Catalyzed by Rhodium(I) Iodide Complexes and Application to Silicon-Containing Polymer Syntheses. / Mori, Atsunori; Takahisa, Eisuke; Yamamura, Yuichi; Kato, Tsuyoshi; Mudalige, Anoma P.; Kajiro, Hiroshi; Hirabayashi, Kazunori; Nishihara, Yasushi; Hiyama, Tamejiro.

In: Organometallics, Vol. 23, No. 8, 12.04.2004, p. 1755-1765.

Research output: Contribution to journalArticle

Mori, Atsunori ; Takahisa, Eisuke ; Yamamura, Yuichi ; Kato, Tsuyoshi ; Mudalige, Anoma P. ; Kajiro, Hiroshi ; Hirabayashi, Kazunori ; Nishihara, Yasushi ; Hiyama, Tamejiro. / Stereodivergent Syntheses of (Z)- and (E)-Alkenylsilanes via Hydrosilylation of Terminal Alkynes Catalyzed by Rhodium(I) Iodide Complexes and Application to Silicon-Containing Polymer Syntheses. In: Organometallics. 2004 ; Vol. 23, No. 8. pp. 1755-1765.
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AU - Mori, Atsunori

AU - Takahisa, Eisuke

AU - Yamamura, Yuichi

AU - Kato, Tsuyoshi

AU - Mudalige, Anoma P.

AU - Kajiro, Hiroshi

AU - Hirabayashi, Kazunori

AU - Nishihara, Yasushi

AU - Hiyama, Tamejiro

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AB - RhI(PPh3)3 or [RhI(cod)]2 (cod = 1,5-cyclooctadiene) as a catalyst delivers both (Z)- and (E)-alkenylsilanes in the stereodivergent hydrosilylation of terminal alkynes with heteroatom-substituted organosilane reagents. Treatment of the rhodium catalyst and the silane reagent followed by addition of terminal alkyne at room temperature leads to (Z)-silanes, while addition of the silane and the alkyne to the rhodium catalyst in one portion and heating at 60°C affords (E)-silanes highly selectively. The obtained (E)- and (Z)-alkenylsilanes bearing heteroatom substituents on the silicon atom are subjected to the palladium-catalyzed cross-coupling reaction with aryl halides to form a carbon-carbon bond with retention of stereochemistry. The stereodivergent hydrosilylations are applied to the polyaddition with bifunctional alkynes (1,3- and 1,4-diethynylbenzene) and silanes (1,3- or 1,4-bis(dimethylsilyl)benzene), giving silicon-containing polymers, poly(aryleneethenylenesilylene)s, in highly stereocontrolled manners. A fluorine-containing silicon reagent bearing a 3,3,3-trifluoropropyl group is also subjected to the polymerization, in which [Rhl(cod)]2 is found to be an efficient catalyst. Measurement of UV-vis absorption/emission spectra and several thermal analyses of the polymers are also conducted.

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