74472-22-3Relevant articles and documents
Novel α,ω-bis(trialkylsilyl)-allyl and -1-azapentadienyl ligands; structures of [Li{η3-CH(CHSiMe2But)2} (tmen)], [Li {N(SiMe3)CBut(CH)3SiMe2Bu t} (tmen)] and [K{η4-N(SiMe2But)CBut(CH) 3SiMe2But}]
Hitchcock, Peter B.,Lappert, Michael F.,Wang, Zhong-Xia
, p. 1647 - 1648 (1996)
The η3-allyl-lithium or -potassium compounds [Li{η3-CH(CHSiMe2But)(CHSiMe 2R)}(tmen)] (R = But 3a, Me 3b) and K{η3-CH(CHSiMe2But)2} (obtained from ButMe2SiCH2CH=CHSiMe2R) with ButCN afford the 1-azapentadienyl-lithium or -potassium compounds [Li{η1-N(SiMe2R)C(But)(CH) 3SiMe2But}L] (L = tmen, R = But 6a, Me 6b; L absent, R = But 8a, Me 8b) or [K{η4-N(SiMe2But)C(But)(CH) 3SiMe2But}]∞ 7.
Mesoporous aluminosilicate-catalyzed allylation of carbonyl compounds and acetals
Ito, Suguru,Hayashi, Akira,Komai, Hirotomo,Yamaguchi, Hitoshi,Kubota, Yoshihiro,Asami, Masatoshi
supporting information; body text, p. 2081 - 2089 (2011/04/19)
A mesoporous aluminosilicate (Al-MCM-41) was found to be an effective heterogeneous catalyst for the reaction of both carbonyl compounds and acetals with allylsilanes to afford the corresponding homoallyl silyl ethers and homoallyl alkyl ethers, respectively. Both the mesoporous structure and the presence of aluminum moiety were indispensable for the high catalytic activity of Al-MCM-41. Moreover, Al-MCM-41 could catalyze the reaction of acetals chemoselectively in the presence of the corresponding carbonyl compounds. The solid acid catalyst Al-MCM-41 could be recovered easily by filtration and could be reused three times without a significant loss of catalytic activity.
Evaluation of β- and γ-Effects of Group 14 Elements Using Intramolecular Competition
Sugawara, Masanobu,Yoshida, Jun-Ichi
, p. 3135 - 3142 (2007/10/03)
To evaluate β-effects and γ-effects of group 14 elements, we have devised a system in which the intramolecular competition between γ-elimination of tin and β-elimination of silicon, germanium, and tin can be examined. Thus, the reactions of α-acetoxy(arylmethyl)stannanes with allylmetals (metal = Si, Ge, Sn) in the presence of BF3·OEt2 were carried out. The reactions seem to proceed by the initial formation of an α-stannyl-substituted carbocation, which adds to an allylmetal to give the carbocation that is β to the metal and γ to tin. The β-elimination of the metal gives the corresponding allylated product, and the γ-elimination of tin gives the cyclopropane derivative. In the case of allylsilane, the cyclopropane derivative was formed as a major product, whereas in the case of allylgermane the allylated product was formed predominantly. In the case of the allystannane the allylated product was formed exclusively. These results indicate that the y-elimination of tin is faster than the β-elimination of silicon, but slower than the β-elimination of germanium and tin. The theoretical studies using ab initio molecular orbital calculations of the carbocation intermediates are consistent with the experimental results. The effect of substituents on silicon was also studied. The introduction of sterically demanding substituents on silicon disfavored the β-elimination of silicon probably because of the retardation of nucleophilic attack on silicon to cleave the carbon-silicon bond.
