RESUMO
Treatment of dialkylbenzylsilanes (1) with trityl tetrakis(pentafluorophenyl)borate (TPFPB) afforded the corresponding silylium ions in equilibrium with their intra- or intermolecular π-complexes, which underwent dehydrogenative annulation with various alkenes to form 1,2,3,4-tetrahydro-2-silanaphthalenes (4) in up to 82% isolated yield. Sterically bulkier substituents on the silicon atom tended to increase the yield of cyclic products 4. The annulation products retained the stereochemistry in cases of the reactions using internal alkenes. The use of diisopropyl(1-naphthyl)silane (2) instead of 1 also resulted in annulation to obtain the 2,3-dihydro-1-sila-1H-phenalene derivatives 6. Electrophilic aromatic substitution at the 8-position was predominant, despite the two potentially reactive positions on the naphthyl group. The steric hindrance of the naphthyl group prevented addition of the cis-alkene to the silylium ion, which would considerably decrease yields of the desired products from 2 compared to those from 1.
RESUMO
Diorganyl[2-(trimethylsilylethynyl)phenyl]silanes 1a-c and methyl-substituted phenylsilanes 1d and 1e were treated with a small amount of trityl tetrakis(pentafluorophenyl)borate (TPFPB) as an initiator in benzene to afford the corresponding benzosiloles (2a-e) in moderate to good yields. However, no reaction was observed for the reaction using [2-(1-hexynyl)phenyl]diisopropylsilane lf. The methyl substituent was tolerated under the reaction conditions and increased the yield of the corresponding benzosilole depending on the substitution position. From the result using 1f, the current reaction was found to require the trimethylsilyl group, which can stabilize intermediary alkenyl carbocations by the ß-silyl effect. The current reaction can be considered an intramolecular chain hydrosilylation of alkynylarylsilanes involving silyl cations as chain carriers. Therefore, the silyl cations generated by hydride abstraction from hydrosilanes 1 with the trityl cation causes intramolecular electrophilic addition to the C-C triple bond to form ethenyl cations, which abstract a hydride from 1 to afford benzosiloles 2 with the regeneration of the silyl cations.
Assuntos
Compostos de Organossilício/síntese química , Silanos/síntese química , Catálise , Estrutura Molecular , Compostos de Organossilício/química , Silanos/químicaRESUMO
Treatment of dialkylbenzylsilane (1) with trityl tetrakis(pentafluorophenyl)borate (TPFPB) in the presence of terminal or internal alkynes (3) and 2,6-di-tert-butyl-4-methylpyridine gave the corresponding 1,2-dihydro-2-silanaphthalene derivatives (4) in 34-82% yields.
RESUMO
The reaction of SnCl(2) with the lithio derivative of a bis(oxazoline) ligand precursor afforded the enantiomeric chlorostannylene whose chloride ion can be substituted by several neutral or anionic Lewis donors. Abstraction of the chloride ion from the chlorostannylene with silver salts gave the corresponding tetrahydrofuran (THF) complexes of a chiral tin(ii) cation in 1,2-dimethoxyethane (DME) containing THF. That is, the reaction with silver hexafluoroantimonate (AgSbF(6)) afforded the THF complex without interaction with the counteranion. In contrast, reaction with silver triflate (AgOTf) gave the THF complex whose tin center had a pseudo-trigonal bipyramidal structure with two nitrogen atoms of a bidentate ligand and a lone pair at the equatorial positions and one of the oxygen atoms of triflate and an oxygen atom of THF at the apical positions in the solid state. Use of 3-methyltetrahydrofuran (3-MeTHF) instead of THF afforded the 3-MeTHF complexes, where the R-enantiomer of 3-MeTHF predominantly coordinates to the tin center. The previously reported germanium(II) analogue of the tin(II) cation indicated a similar enantioselectivity for the coordination of 3-MeTHF on the germanium center.
RESUMO
Zero-valence platinum complex [Pt(dppe)(eta(2)-C(2)H(4))] (1, dppe = 1,2-bis(diphenylphosphino)ethane) treated with disilanes HR(1)R(2)SiSiMe(3) (a, R(1) = R(2) = Me; b, R(1) = R(2) = Ph; c, R(1) = H, R(2) = Ph) afforded the corresponding disilanylplatinum hydrides [Pt(dppe)(H)(SiR(1)R(2)SiMe(3))] (2a-c) by oxidative addition of the Si-H bond to the platinum center. The 1,2-silyl migration in 2a,b led to the formation of bis(silyl)platinum complexes [Pt(dppe)(SiHR(1)R(2))(SiMe(3))] (3a,b) with a first-order rate constant of 7.2(2) x 10(-4) s(-1) at 25 degrees C for 2a and 3.86(4) x 10(-4) s(-1) at 40 degrees C for 2b, whereas 2c with R(1) = H followed by the transient generation of 3c dimerized rapidly to give the bis(mu-silylene)diplatinum complex [Pt(dppe)(mu-SiHPh)](2) (4c) in a mixture of cis/trans isomers. Heating of the toluene solution of 3b at 100 degrees C resulted in a similar dimerization to 4b. In addition, a trinuclear platinum complex [Pt(3)(dppe)(3)(mu(3)-SiPh)(2)] (5) with a trigonal bipyramidal Pt(3)Si(2) core arose from the reaction of 4c with 1 at 60 degrees C in toluene. Unsymmetric disilanes therefore accomplished the syntheses of various monomeric and dimeric platinum complexes via 1,2-hydrogen and silyl migration to the platinum center.