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

1.在亚磷酸三乙酯存在下，硫代缩醛与茂钛(II)物种反应生成的钛卡宾配合物与乙烯反应生成一碳同源末端烯烃。在没有亚磷酸三乙酯的情况下进行反应，可生成多两个碳的末端烯烃。当卡宾络合物与苯乙烯衍生物反应时，也观察到后一类反应。2.卡宾络合物与丙戊酸乙酯的反应通过中间体环丙基钛物种选择性地生成环丙烷。3.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产生了还原的烷基化产物--无环胺和环胺。4.含β-取代基的卤代烷与茂钛(II)试剂反应生成了钛-卡宾络合物，其中…更多的依赖于β取代基的体积。这些钛试剂被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-茂钛(II)体系进行类似的羰基烯化反应，得到了多种烯醇醚。5.二(苯硫基)甲基三丁基锡烷与锂醇盐的氧化偶联反应生成了二硫代原甲酸酯。这些化合物与二茂钛(II)物种反应得到烷氧亚甲基基钛烯化合物，这使烯醇醚与包括羧酸衍生物的羰基化合物反应。6.用二茂钛(II)试剂处理炔基硫代缩醛生成的炔基卡宾络合物与末端烯烃反应得到炔基环丙烷。在利用在α-位置上具有三烷基硅基的炔基硫代缩醛的反应的情况下，环丙烷化反应区域选择性地发生在γ-位置。类似地，利用α-三烷基硅烷基-炔基硫代缩醛进行的羰基烯化反应优先生成1-三烷基硅烷-3-烯-1-YNES。7.硫代缩硅醛与乙炔生成的钛卡宾络合物与乙炔反应生成聚乙炔作为独立的导电膜。较少

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