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Exploration of Unique Reactivity of Organotitanocene Complexes and Its Application to Organic Synthesis

有机二茂钛配合物独特反应活性的探索及其在有机合成中的应用

基本信息

批准号：
14340228
负责人：
TAKEDA Takeshi
金额：
$ 8.26万
依托单位：
National University Corporation Tokyo University of Agriculture and Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2004
项目状态：
已结题

项目摘要

1.In the presence of triethyl phosphite, titanium carbene complexes generated by the reaction of thioacetals with a titanocene(II) species reacted with ethylene to produce terminal olefins with one carbon homologation. When the reaction was carried out in the absence of triethyl phosphite, terminal olefins with two more carbons were produced. The latter type reaction was also observed when the carbene complexes were treated with styrene derivatives.2.The reaction of the carbene complexes with vinyl pivalate selectively gave cyclopropanes via the intermediary cyclopropyltitanium species. Vinylcyclopropanes were also obtained by the reaction of carbene complexes with 1,3-dienes.3.The titanocene(II)-promoted inter-and intra-molecular reactions of thioacetals with anilides produced reductive alkylation products, acyclic and cyclic amines, respectively.4.The reaction of alkyl halides bearing a β-substituent with the titanocene(II) reagent produced titanium carbene complexes, yields of which … More were dependent on the bulkiness of β-substituent. These titanium reagents were successfully applied to the olefination of various carbonyl compounds. Similar carbonyl olefination utilizing an alkyl chloromethyl ether-titanocene(II) system gave a variety of enol ethers.5.The oxidative coupling of bis(phenylthio) methyltributylstannane with lithium alkoxides produced dithioorthoformates. Treatment of these compounds with the titanocene(II) species afforded alkoxymethylidenetitanocenes, which gave enol ethers on treatment with carbonyl compounds including carboxylic acid derivatives.6.The reaction of alkynylcarbene complexes, generated by the treatment of alkynyl thioacetals with the titanocene(II) reagent, with terminal olefins gave alkynylcyclopropanes. In the case of the reaction utilizing the alkynyl thioacetals having a trialkylsilyl group at α-position, the cyclopropanation regioselectively occurred at γ-position. Similarly the carbonyl olefination utilizing α-trialkylsilyl alkynyl thioacetals produced 1-trialkylsilylalk-3-en-1-ynes preferentially.7.The treatment of titanium carbene complexes generated from thioacetals with acetylene produced polyacetylene as free-standing conducting films. Less

1.在亚磷酸三乙酯存在下，由硫代缩醛与二茂钛（II）反应生成的钛卡宾配合物与乙烯反应生成具有一个碳同系化的末端烯烃。当反应在不存在亚磷酸三乙酯的情况下进行时，产生具有两个以上碳的末端烯烃。2.卡宾配合物与新戊酸乙烯酯的反应通过中间体环丙基钛选择性地生成环丙烷类化合物。二茂钛（II）促进的硫代缩醛与苯胺的分子间和分子内反应分别生成还原性烷基化产物、无环胺和环胺; 4.带有β-取代基的卤代烷与二茂钛（II）试剂反应生成钛卡宾配合物，产率分别为100%和100%; 5.二茂钛（II）促进的硫代缩醛与苯胺的分子间和分子内反应分别生成还原性烷基化产物、无环胺和环胺; 6.二茂钛（II）促进的硫代缩醛与苯胺的分子间和分子内反应分别生成还原性烷基化产物、无环胺和环胺 ...更多信息与β-取代基的体积有关。这些钛试剂已成功地应用于各种羰基化合物的烯化反应。利用烷基氯甲醚-二茂钛（II）体系进行类似的羰基烯化反应，得到了多种烯醇醚。5.双（苯硫基）甲基三丁基锡烷与锂醇盐氧化偶联生成二硫代原甲酸酯。这些化合物与二茂钛（II）反应生成烷氧基亚甲基二茂钛（II），后者与羰基化合物（包括羧酸衍生物）反应生成烯醇醚。6.炔基卡宾配合物由炔基硫代缩醛与二茂钛（II）反应生成，与末端烯烃反应生成炔基环丙烷。在使用在α-位具有三烷基甲硅烷基的炔基硫代缩醛的反应的情况下，环丙烷化区域选择性地发生在γ-位。同样，α-三烷基硅炔基硫代缩醛的羰基烯化反应优先生成1-三烷基硅烷基烷-3-烯-1-炔。7.硫代缩醛生成的钛卡宾配合物与乙炔反应生成聚乙炔自支撑导电膜。少