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 language | English |
|---|---|
| Pages (from-to) | 1755-1765 |
| Number of pages | 11 |
| Journal | Organometallics |
| Volume | 23 |
| Issue number | 8 |
| DOIs | |
| Publication status | Published - Apr 12 2004 |
| Externally published | Yes |
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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 journal › Article
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TY - JOUR
T1 - 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
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
PY - 2004/4/12
Y1 - 2004/4/12
N2 - 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.
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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U2 - 10.1021/om049922r
DO - 10.1021/om049922r
M3 - Article
AN - SCOPUS:2342444385
VL - 23
SP - 1755
EP - 1765
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 8
ER -