Bimolecular Reactions of Tetrakis(trialkylsilyl)disilenes with Various Reagents
Bimolecular Reactions of Tetrakis(trialkylsilyl)disilenes with Various Reagents
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四(三烷基甲硅烷基)二硅烯与各种试剂的双分子反应
DOI：
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发表时间：
1998
期刊：
影响因子：
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通讯作者：
M. Kira
中科院分区：
文献类型：
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作者：
T. Iwamoto;H. Sakurai;M. Kira
已经公开了四甲硅烷基二硅烯与各种试剂的多种反应模式。通常，四(叔丁基二甲基甲硅烷基)二硅烯1b与1-烯烃和具有烯丙基氢的1-炔反应得到相应的烯加成产物，而1b与苯乙烯反应得到[2+2]环加成产物。与四叔丁基二硅烯和四均三甲基二硅烯相反，1b与1,3-丁二烯的反应定量地给出[4+2]环加成产物。根据理论上预测的二硅烯的双自由基性质，四甲硅烷基二硅烯1b可能通过自由基机理与卤代烷反应生成相应的2,3-二氯四硅烷或2-烷基-3-氯四硅烷。水、甲醇和甲基锂对1b的轻松亲核加成表明1b具有高亲电性。
Versatile reaction modes of tetrasilyldisilenes with various reagents have been disclosed. Typically, tetrakis(t-butyldimethylsilyl)disilene 1b reacts with 1-alkenes and a 1-alkyne having allylic hydrogens to afford the corresponding ene-addition products, while a reaction of 1b with styrene gives the [2+2] cycloaddition product. In contrast to tetra-t-butyldisilene and tetramesityldisilene, a reaction of 1b with a 1,3-butadiene gives quantitatively the [4+2] cycloaddition product. In accord with the biradical nature of disilene as predicted theoretically, tetrasilyldisilene 1b reacts with haloalkanes to provide the corresponding 2,3-dichlorotetrasilane or 2-alkyl-3-chlorotetrasilane probably via radical mechanisms. Facile nucleophilic additions of water, methanol, and methyllithium to 1b are indicative of the high electrophilicity of 1b.