Group VIII metal phosphine complexes-catalyzed addition of disilanes to allenic compoundsFormation of new organosilicon compounds containing both vinylsilane and allylsilane units
catalyst gave regioselectively new functionalized organosiliconcompounds, 2, 3-bis(organosilyl)prop-1-enes and 2, 3-bis(organosilyl)but-1-enes, respectively. Other group VIII metal-phospine complexes also affected the reaction, but results were found to be less satisfactory. Also, the reaction of any unsymmetrical disilane with an allenic compound gave only a single product; e.g., the addition of
将氯甲基-和甲氧基甲基乙硅烷X 3 - m Me m SiSiMe n -X 3 - n(X-Cl和OMe; m,n -0-2)以及六甲基乙硅烷添加到丙二烯和1,2-丁二烯中Pd(PPh 3)4的存在催化剂分别产生区域选择性的新型官能化有机硅化合物,2,3-双(有机甲硅烷基)丙-1-烯和2,3-双(有机甲硅烷基)丁-1-烯。其他族金属-膦配合物也影响了反应,但结果却不令人满意。同样,任何不对称的乙硅烷与烯丙基化合物的反应只能得到单一产物。例如,在Pd(PPh 3)4存在下向1,2-丁二烯中添加氯五甲基二硅烷,得到CH 2 -C(SiMe 3)CH(SiMe 2 Cl)Me,产率为93%。
Double silylation of allene and buta-1,2-diene: formation of new organosilicon compounds containing both vinylsilane and allylsilane units
Addition of chloromethyl-and methoxymethyl-disilanes, as well as hexamethyldisilane, to allene and buta-1,2-diene in the presence of a Pd (PPh3)4 catalyst gave, regioselectively, new functionalized organosilicon compounds, 2,3-bis(organosily)prop-1-enes and 2,3-bis-(organosilyl)but-1-enes, respectively.
Organodisilanes, Me3-nXnSiSiXnMe3-n (X = Cl and MeO, n = 0, 1, 2) undergo efficient 1:2 addition reactions with butadiene and isoprene in the presence of a catalytic amount of a suitable palladium complex. One of the products, the title compound, was used as a starting material for a short synthesis of dl-muscone.
In the presence of a palladium(0) complex catalyst, methoxymethyldisilanes, (MeO)n Me3-nSiSiMe3-m (OMe)m (m, n 1, 2), added to 1-hexyne, trimethylsilyl-acetylene and acetylene to give double silylation products, 1,2-bis(methoxy-methylsilyl)olefins, in varying yields.
Silylene chemistry II. A kinetic study of the thermolysis of sym-dimethoxytetramethyldisilane
作者:William H. Atwell、Louis G. Mahone、Steven F. Hayes、John G. Uhlmann
DOI:10.1016/s0022-328x(00)80234-x
日期:1969.7
study of the thermolysis of sym-dimethoxytetramethyldisilane (I) has been carried out. This study provides strong support for our previous proposal that dimethyldimethoxysilane and dimethylsilylene are formed in an unimolecular and rate determining a-elimination step. Further, chemical evidence is reported which, for the first time, clearly and unambiguously demonstrates insertion of silylenes into the