Stereochemistry of the addition of dimethylsilylene to cis- and trans-2-butene

Tortorelli, Victor J.; Jones, Maitland

doi:10.1021/ja00524a038

Cited by 31 publications

(11 citation statements)

References 1 publication

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“…Stereospecific cis addition to olefins has been reported for dimethylsilylene, Me 2 Si:, − phenyltrimethylsilylsilylene, Ph(Me 3 Si)Si:, diphenylsilylene, Ph 2 Si:, and diadamantylsilylene, Ad 2 Si:, all presumed to have reacted from their ground singlet electronic states.…”

Section: Discussionmentioning

confidence: 98%

Tris(triisopropylsilyl)silane and the Generation of Bis(triisopropylsilyl)silylene

Gaspar¹,

Beatty²,

Chen³

et al. 1999

Organometallics

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Tris(triisopropylsilyl)silane (iPr 3 Si) 3 SiH has been synthesized and studied by X-ray and neutron diffraction. It possesses an unusual structure in which the four silicon atoms are nearly coplanar, ∠Si-Si-Si ) 118.41(5)°. The Si-H distance is found to have a normal value of 1.506(2) Å. Thermal and room-temperature photochemical decomposition of (iPr 3 -Si) 3 SiH leads to the elimination of iPr 3 SiH and the generation of bis(triisopropylsilyl)silylene, [(iPr 3 Si) 2 Si:]. Reactions of (iPr 3 Si) 2 Si: include precedented insertions into H-Si bonds and addition to the π-bonds of olefins, alkynes, and dienes. Despite theoretical predictions of a triplet ground state for [(iPr 3 Si) 2 Si:], stereospecific addition to cis-and trans-2-butene was observed.

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Section: Discussionmentioning

confidence: 98%

Tris(triisopropylsilyl)silane and the Generation of Bis(triisopropylsilyl)silylene

Gaspar¹,

Beatty²,

Chen³

et al. 1999

Organometallics

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“…If lithium reagent 4 had undergone intramolecular nucleophilic attack at an iron atom, followed by Fe-P heterolysis, a phosphide anion would result. Two modes of (7) Anal Caled for C^H^OgFe^: C, 52.81; H, 3.28. Found: C, 52.80; H, 3.39.…”

Section: Communicationsmentioning

confidence: 99%

“…(4) The analytical sample was recrystallized from CH2Cl2/petroleum ether and was found to be a 1:1 CH2C12 solvate: NMR (CDC13) 3.11-3.68 (br m, CH2, 4 ), 7.02-7.73 (complex m, arene H); 31P NMR (CHCls) 136.2; IR (CHC13) v(C=0) 2047 (s), 2010 (vs), 1983 (s), 1967 (s) cm"1. Anal.…”

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confidence: 99%

Intramolecular nucleophilic attack at iron in an anionic phosphido-bridged hexacarbonyldiiron [Fe2(CO)6] complex

Seyferth¹,

Wood²,

Fackler³

et al. 1984

Organometallics

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“…The formation of 4a , b and 5a , b may be best understood by the reaction of the silabicyclobutane derivative ( A or A′ ), generated photochemically directly from 2 or 3 , with tert -butyl alcohol and tert -butyl alcohol- d 1 , respectively, as shown in Scheme . The silabicyclobutanes A and A′ thus formed presumably are labile under the photolysis conditions used, and some of them would undergo decomposition to give the unidentified products.…”

Section: Resultsmentioning

confidence: 99%

Silicon−Carbon Unsaturated Compounds. 76. Photochemical and Thermal Behavior of 1-Silacyclobut-3-enes Generated from the Reaction of Pivaloyltris(trimethylsilyl)silane with tert-Butylacetylene

et al. 2009

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Irradiation of trans-1-silacyclobut-3-ene 2, obtained by thermal isomerization of [2 þ 2] cycloadduct 1 arising from the co-thermoysis of pivaloyltris(trimethylsilyl)silane with tert-butylacetylene, with a low-pressure mercury lamp afforded an equilibrium mixture consisting of 2 and its isomer, cis-1-silacyclobut-3-ene 3, in a ratio of 1:1. Similar irradiation of the cis isomer 3 gave the mixture involving equal amounts of 2 and 3. The photolysis of 2 in the presence of tert-butyl alcohol gave two isomers of the cyclopropane derivative, arising from the reaction of silabicyclobutane, A and A 0 , with alcohol. The thermolysis of 3 at 250 °C produced 2 in quantitative yield. Similar thermolysis of 3 in the presence of tert-butyl alcohol, however, afforded no alcohol adducts, but 2 was obtained as the sole product. The DFT calculations with the use of cis-2,4-dimethyl-1-siloxy-1,2-bis(silyl)-1-silacyclobut-3-ene as a starting compound and trans-2,4-dimethyl-1-siloxy-1,2-bis(silyl)-1-silacyclobut-3ene as a product indicated that a pentacoordinate silicon intermediate plays an important role in the thermal isomerization of 3 to 2.

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Stereochemistry of the addition of dimethylsilylene to cis- and trans-2-butene

Cited by 31 publications

References 1 publication

Tris(triisopropylsilyl)silane and the Generation of Bis(triisopropylsilyl)silylene

Tris(triisopropylsilyl)silane and the Generation of Bis(triisopropylsilyl)silylene

Intramolecular nucleophilic attack at iron in an anionic phosphido-bridged hexacarbonyldiiron [Fe2(CO)6] complex

Silicon−Carbon Unsaturated Compounds. 76. Photochemical and Thermal Behavior of 1-Silacyclobut-3-enes Generated from the Reaction of Pivaloyltris(trimethylsilyl)silane with tert-Butylacetylene

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