Organic Synthesis using Silicone as all Organosilicon Reagent

以有机硅为有机硅试剂的有机合成

• 批准号: 13650915
• 负责人: MORI Atsunori
• 金额: $ 2.3万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650915/
• 关键词: silicone; organosilicon reagent; cyclic siloxane; polysiloxane; cross-coupling reaction; conjugate addition; tetrabutylammonium fluoride; Mizoroki-Heck-type reaction; 酸化銀

This research pursued for the purpose of carrying out synthetic organic reactions using silicone as a new class of organosilicon reagent. Silicone bearing an aryl or alkenyl group on the silicon atom was employed for several carbon-carbon bond-forming reactions. Cyclic or polymeric silicone reagent was use for the reaction. In particular, poly (phenylmethylsiloxane), which is a commercially available highly thermo-resistant silicone oil, affected palladium-catalyzed cross-coupling reaction with organic halides to give biaryl derivatives that are potentially available for liquid crystalline organic materials. Alkenylsiloxanes, which was prepared from commercially available PMHS ; poly (methylhydrosiloxane) with alkyne via hydrosilylation, also affected cross-coupling reactions. In these reactions TBAF (tetrabutylammonium fluoride) or Ag_2O served as an effective activator for the reaction. Rhodium-catalyzed reaction of alfa. Beta-unsaturated carbonyl compounds also took place to give the conjugate addition products. On the other hand, the reaction of organosilicon reagents catalyzed by indium complexes brought about the Mizoroki-Heck-type reaction.

本研究旨在利用有机硅作为一类新型有机硅试剂进行有机合成反应。硅原子上含有芳基或烯基的有机硅被用于几个碳-碳键的形成反应。反应采用环状或聚合型有机硅试剂。特别是，聚(苯甲基硅氧烷)是一种商业上可获得的高度耐热的硅油，它影响了钯催化的与有机卤化物的交叉偶联反应，得到了可能用于液晶有机材料的联芳基衍生物。由市售PMHS制备的烯基硅氧烷；聚甲基氢化硅氧烷与炔通过硅氢加成反应也影响交叉偶联反应。在这些反应中，四丁基氟化铵(TBAF)或Ag_2O是反应的有效活化剂。Rh催化的α-丙二醛反应。还发生了β-不饱和羰基化合物的共轭加成反应。另一方面，有机硅试剂在铟配合物的催化下发生了Mizoroki-Heck反应。

项目成果

A. Mori: "Latest Frontiers of Organic Synthesis"New synthetic reactions using silanols and siloxanes. 19 (2003)

A. Mori：“有机合成的最新前沿”使用硅烷醇和硅氧烷的新合成反应。

Y. Yamamura: "Chirality transfer from silicon to carbons via diastereoselective Simmons-Smith cyclopropanation of chiral alkenylsilanols"Tetrahedron Asymmetry. 1-13. 13-15 (2002)

Y. Yamamura：“通过手性烯基硅烷醇的非对映选择性西蒙斯-史密斯环丙烷化从硅到碳的手性转移”四面体不对称性。

T. Koike: "Iridium-catalyzed Mizoroki-Heck-type reaction of organosilicon reagents"Angew. Chem., Int. Ed.. 1-42. 89-92 (2003)

T. Koike：“有机硅试剂的铱催化 Mizoroki-Heck 型反应”Angew。

A.Mori: "[Rh(OH)(cod)]2 (cod=1,5-cyclooctadiene), a highly efficient catalyst for 1,4-hydrosilylation of alfa, beta-unsaturated carbonyl compounds"Synlett. 7. 1169-1171 (2002)

A.Mori：“[Rh(OH)(cod)]2（cod=1,5-环辛二烯），一种用于 α、β-不饱和羰基化合物 1,4-氢化硅烷化的高效催化剂”Synlett。

T.Fujii: "Rhodium-catalyzed addition of aryl-and alkenylsilanediols to aldehydes"Synlett. ・2. 298-300 (2002)

T.Fujii：“芳基和烯基硅烷二醇与醛的铑催化加成”Synlett ・298-300 (2002)。