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Development of Novel Synthetic Reactions Based on the Activation of the Third Row Elements'

基于第三行元素活化的新型合成反应的发展

基本信息

批准号：
07405042
负责人：
HIYAMA Tamejiro
金额：
$ 21.31万
依托单位：
KYOTO UNIVERSITY (1997-1998)Tokyo Institute of Technology (1995-1996)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1998
项目状态：
已结题

项目摘要

(1) Oxidative Desulfurization FluorinationUpon reaction with an oxidant like a positive halogen, organosulfur compounds gives sulfonium ions whose C-S bonds are weaked to undergo nucleophilic substitution readily. A fluoride ion of 70% HF/Py and Bu_4NH_2F_3 replaces sulfur to give organofluorine compounds. In this way, trifluoromethyl-substituted aromatics and olefins, trifluoromethyl ethers, trifluoromethylamines, alpha-fluoro sulfides, and vis-difluoro olefins are shown to be readily available from the corresponding organosulfur precursors.(2) Cross-Coupling Reactions with Organosilicon CompoundsThis novel reaction is now called as the Hiyama Coupling. Although a trimethylsilyl group is pertinent to vinylsilanes, SiFMe_2 or SiF_2 Me is necessary for alkenylsilanes in general.Alkoxysilanes also are applicable. As a coupling partner, aryl chlorides are now shown to be applicable.Transmetalation from silicon to copper(I) is now achieved in DMF.Thus, alkynylsilanes couple with halobenzenes or dimerizes oxidatively using a palladium catalyst. Conjugate reduction of alpha, beta-unsaturated esters and ketones is attained with hydrosilanes.(3) Cross-Coupling and Carbostannylation with Organotin CompoundsUsing a novel catalyst consisting of palladium and an imino phosphine ligand, organotin compounds are shown to readily undergo cross-coupling reactions, oxidative dimerization, and carbostannylation to acetylenes.

(1)氧化脱硫氟化有机硫化合物与氧化剂（如正卤素）反应后，会产生锍离子，其C-S键被削弱，易于进行亲核取代。70%HF/Py和Bu_4NH_2F_3的氟离子取代硫得到有机氟化合物。以这种方式，三氟甲基取代的芳族化合物和烯烃、三氟甲基醚、三氟甲基胺、α-氟硫化物和顺式-二氟烯烃显示出容易从相应的有机硫前体获得。(2)与有机硅化合物的交叉偶联反应这种新的反应现在被称为Hiyama偶联。虽然三甲基硅烷基与乙烯基硅烷有关，但SiFMe_2或SiF_2Me一般是烯基硅烷所必需的，烷氧基硅烷也是适用的。作为一种偶联伙伴，芳基氯现在被证明是适用的。从硅到铜（I）的金属转移现在在DMF中实现。因此，炔基硅烷与卤代苯偶联或使用钯催化剂氧化二聚。用氢化硅烷实现α，β-不饱和酯和酮的共轭还原。(3)使用由钯和亚氨基膦配体组成的新型催化剂，有机锡化合物显示出容易进行交叉偶联反应、氧化二聚和甲锡羰化为乙炔。