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

1.在亚磷酸三乙酯存在下，硫缩醛与二茂钛（II）反应生成的碳钛配合物与乙烯反应生成一碳同源的末端烯烃。在没有亚磷酸三乙酯的情况下进行反应，生成了多两个碳的末端烯烃。当用苯乙烯衍生物处理羰基配合物时，也观察到后一种反应。羰基配合物与戊酸乙烯酯反应，通过中间环丙基钛选择性生成环丙烷。由1,3-二烯与羰基配合物反应得到乙烯基环丙烷。二茂钛（II）促进了硫缩醛与苯胺的分子间反应和分子内反应，分别生成还原性烷基化产物无环胺和环胺。含β-取代基的烷基卤化物与二茂钛（II）试剂反应生成羰基钛配合物，其产率主要取决于β-取代基的体积。这些钛试剂成功地应用于各种羰基化合物的烯化。类似的羰基烯化利用烷基氯甲基醚-二茂钛（II）体系得到了多种烯醇醚。二（苯基硫）甲基三丁基锡烷与烷氧锂氧化偶联生成二硫代原甲酸盐。这些化合物用二茂钛（II）类处理得到烷氧基甲基二茂钛，用羰基化合物包括羧酸衍生物处理得到烯醇醚。用二茂钛（II）试剂处理炔基硫缩醛生成炔基羰基配合物，与末端烯烃反应得到炔基环丙烷。在α-位置有三烷基硅基的炔基硫缩醛反应中，环丙化区选择性地发生在γ-位置。同样，利用α-三烷基硅烷酰缩硫醛的羰基烯烃也优先产生1-三烷基硅烷-3-烯-1-炔。用乙炔处理硫缩醛生成的羰基钛配合物，制备聚乙炔作为独立导电薄膜。少

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