Design, Synthesis, and Implementation of Sodium Silylsilanolates as Silyl Transfer Reagents
Design, Synthesis, and Implementation of Sodium Silylsilanolates as Silyl Transfer Reagents
复制标题
甲硅烷基硅烷醇钠作为甲硅烷基转移试剂的设计、合成和实现
DOI：
10.1021/acscatal.1c02733
复制
发表时间：
2021
期刊：
影响因子：
12.9
通讯作者：
Yorimitsu Hideki
中科院分区：
文献类型：
--
作者：
Yamagishi Hiroki;Saito Hayate;Shimokawa Jun;Yorimitsu Hideki
对于将甲硅烷基轻松递送到有机生物活性分子上的需求日益增长。通过过渡金属催化的偶联反应进行硅烷化的常见方法之一采用氢硅烷、乙硅烷和甲硅烷基硼烷作为主要硅源。然而，试剂的不稳定性质或苛刻的反应条件有时使其不足以达到目的。因此，需要一种更通用的甲硅烷基替代源。我们在此报告了可储存硅基硅烷醇钠的设计、合成和实施，该钠可用于在钯催化剂存在下芳基卤化物和拟卤化物的甲硅烷基化。所开发的方法允许对具有各种甲硅烷基的多官能化化合物进行后期官能化。机理研究表明：(1) 亲核硅醇盐攻击钯中心，得到甲硅烷醇盐配位的芳基钯中间体；(2) 硅醇盐物质的聚合簇有助于甲硅烷基的分子内迁移，从而促进有效的金属转移。
There is an increasing demand for facile delivery of silyl groups onto organic bioactive molecules. One of the common methods of silylation via a transition-metal-catalyzed coupling reaction employs hydrosilane, disilane, and silylborane as major silicon sources. However, the labile nature of the reagents or harsh reaction conditions sometimes render them inadequate for the purpose. Thus, a more versatile alternative source of silyl groups has been desired. We hereby report a design, synthesis, and implementation of storable sodium silylsilanolates that can be used for the silylation of aryl halides and pseudohalides in the presence of a palladium catalyst. The developed method allows a late-stage functionalization of polyfunctionalized compounds with a variety of silyl groups. Mechanistic studies indicate that (1) a nucleophilic silanolate attacks a palladium center to afford a silylsilanolate-coordinated arylpalladium intermediate and (2) a polymeric cluster of silanolate species assists in the intramolecular migration of silyl groups, which would promote an efficient transmetalation.