Organic synthesis via Organosilicon-Transition Metal Combined Systems

通过有机硅-过渡金属组合系统进行有机合成

• 批准号: 05453137
• 负责人: TAMAO Kohei
• 金额: $ 4.03万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05453137/
• 关键词: transition-metal catalyst; thermal degradation; pentacoordinated disilane; skeletal rearrangement; (alkoxy) oligosilane; silylene; 有機ケイ素; 遷移金属錯体触媒; 五配位ヒドロシラン; 五配位ポリシラン; 分子内ヒドロシリル化; 脱水素シリル化; 不斉合成; ダブルシリル化; 過酸化水素酸化

1. A pentacoordinated ethoxydisilane, which contains the 8-dimethylamino-1-naphthyl group and ethoxy group on the same silicon atom, was prepared. The X-ray structure analysis revealed that the geometry of the particular silicon atom was deformed from tetrahedral to trigonal bipyramidal. The ethoxydisilane underwent thermal degradation readily at 90ﾟC in DMF or at 110ﾟC in toluene to form ethoxysilane in high yields. The resulting silylene species was trapped efficiently with 2,3-dimethylbutadiene and diphenylacetylene to form the corresponding adducts in high yields. A similar degradation occurred under much milder condition at 50ﾟC in the presence of a Ni (0) or Pd (0) complex as catalyst.2.Poly (alkoxy) trisilanes and tetrasilanes were prepared readily by a new method. These oligosilanes were found to undergo skeletal rearrangement in the presence of Pd (PPh_3)_4 as a catalyst at 80-140ﾟC in the fashion that the internal silylene moiety transferred to the terminal positions. Ten substrates were examined. Typically, 1,2,3- (MeO)_3Me_5Si_3 and 1,2,3,4- (MeO)_4Me_6Si_4 were converted into the 1,1,3-isomer and 1,1,4,4-isomer, respectively, in quantitative yield. A proposed mechanism involved silylene transfer via a bis (silyl) (silylene) Pd complex as a key intermediate.

1。在同一硅原子上含有8-二甲基氨基-1-萘基和乙氧基硅烷的五氧基二硅烷。 X射线结构分析表明，特定硅原子的几何形状从四面体到三角形双锥体形成。乙氧基二硅烷在DMF中很容易在90°C或甲苯中的110°C下进行热降解，以高产量形成乙氧基硅烷。用2,3-二甲基丁二烯和二苯基乙炔有效地将所得的西里烯物种有效地捕获，以高产量形成相应的加合物。在有Ni（0）或Pd（0）复合物存在下，在50°C的许多Miller条件下发生了类似的降解。在PD（PPH_3）_4存在的情况下，这些寡聚烷被发现以80-140 c的催化剂的形式以内部甲硅烷基部分转移到终端位置的方式进行骨骼重排。检查了十个底物。通常，将1,2,3-（MEO）_3ME_5SI_3和1,2,3,4-（MEO）_4ME_6SI_4分别以定量的收益率转换为1,1,3-ISOMER和1,1,3-ISOMER和1,1,4,4-ISOMER。提出的机制涉及通过BIS（Silyl）（Silylene）PD复合物作为关键中间体的甲硅烷基转移。