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Development of New Catalytic Reactions Involving Silylmetalation as a Key Step

以甲硅烷基金属化为关键步骤的新型催化反应的开发

基本信息

批准号：
06805078
负责人：
CHATANI Naoto
金额：
$ 1.47万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1994
资助国家：
日本
起止时间：
1994 至 1995
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06805078/
关键词：
Silylmetalation Iodotrimethylsilane Germyl Cyanide Vinylsilane Coupling アセチレンパラジウム

项目摘要

The aim of this project was to develop new catalytic reactions involving silylmetalation as a key step. I found the following new reactions.1.The reaction of terminal acetylenes with Me_3SiI (1) and organozinc reagents in the presence of Pd (PPh_3)_4 results in addition of the trimethylsilyl group of 1 and an alkyl group of the organozinc reagent to the acetylenes. In all cases the trimethylsilyl group adds to the terminal carbon of the acetylenes. Both aromatic and aliphatic terminal acetylenes undergo the coupling reaction with high regio- and stereoselectivities. The yield and stereoselectivity are relatively sensitive to the nature of the organozinc reagent used. The reaction of phenylacetylene using Bu_2Zn gives the corresponding coupling product in high yield with high stereoselectivity (>98%). In contrast, the use of BuZnI results in 92% stereoselectivity. The stereoselectivity for the reaction using (Me_3SiCH_2)_2Zn is lower than those for Me_2Zn, Et_2Zn, and Bu_2Zn.2.The palladium-catalyzed reaction of trimethylgermyl cyanide (Me_3GeCN,2) with terminal acetylenes is studied in detail with particular emphasis focused on functional group compatibility as well as the factor affecting stereoselectivity. The reaction of 2 with terminal aromatic acetylenes in the presence of PdCl_2 results in the addition of 2 to the carbon-carbon triple bonds with high regioselectivity leading to beta-cyano vinylgermanes in high yields. The stereoselectivity depends on the electronic nature of the substituents on the aromatic ring. The reaction of terminal aliphatic acetylenes also afford the adduct with high regio-and stereoselectivity.

该项目的目的是开发新的催化反应，包括甲硅烷基金属化作为一个关键步骤。1.在Pd（PPh_3）_4存在下，Me_3SiI（1）和有机锌试剂与端炔反应，得到1的三甲基硅基和有机锌试剂的烷基加成到端炔上。在所有情况下，三甲基甲硅烷基都加到乙炔的末端碳上。芳族和脂肪族末端炔均以高的区域和立体选择性进行偶联反应。产率和立体选择性对所用有机锌试剂的性质相对敏感。苯乙炔与Bu_2Zn反应，得到了高产率的偶联产物，立体选择性大于98%。相比之下，使用BuZnI导致92%的立体选择性。（Me_3SiCH_2）_2Zn的立体选择性低于Me_2Zn、Et_2Zn和Bu_2Zn。2.详细研究了钯催化的三甲基锗腈（Me_3GeCN，2）与末端乙炔的反应，着重考察了官能团相容性以及影响立体选择性的因素。在PdCl_2存在下，2与末端芳炔反应，以高的区域选择性将2加成到碳-碳三键上，高产率地得到β-氰基乙烯基锗烷。立体选择性取决于芳环上取代基的电子性质。末端脂肪炔的反应也提供了高区域和立体选择性的加成物。