Transition-metal Catalyzed Oraganic Reactions involving Vinylidene-metal Complexes

涉及亚乙烯基金属配合物的过渡金属催化有机反应

• 批准号: 07805082
• 负责人: OHE Kouichi
• 金额: $ 1.41万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07805082/
• 关键词: Vinylidene; Enediyne; Cycloaromatization; Rhodium-Complex; Saito-Myers Reaction; Saito-Myers環化; Bergmun環化; Myers環化; ビニリデン錯体; 1,4-有機ロジウムジラジカル

Transition-metal can act as a trigger for cycloaromatization of an enediyne. In the presence of Et_3N and 5 mol% [RhCl (i-Pr_3P) _2] catalyzes the reaction of the acyclic enediyne to produce aromatic hydrocarbon. The cyclization similar to Saito-Myers reaction proceeds via vinylidene-rhodiumn and 1,4-organorhodium diradical to afford the product.Cycloaromatization of acyclic enediynes triggered by rhodium (I) catalyst followed by radical cascade reaction with alkenes providing a new C-C bond has been also examined. In the presence of Et_3N and [RhCl (i-Pr_3P) _2], (Z) -3-dodecene-1,5-diyne slowly added by a syringe pump reacted with ethyl acrylate in benzene at 80 ﾟC to give ethyl 3- [2- (1- (E) -propenyl) phenyl] propanoate in 53% isolated yield. The similar reactions with other alkenes, such as ethyl methacrylate, methyl vinyl ketone, and dimethyl maleate took place to give the corresponding adducts in moderate to good yields. Exclusive formation of E-olefinic product was observed in all cases. The example of rhodium-catalyzed tandem C-C bond forming reaction with ethyl acrylate was also observed for the reaction of (Z) -1-cyclohexylhex-3-ene-1,5-diyne and (Z) -1-tert-butyldimethylsilyloxyoct-5-ene-3,7-diyne leading to the formation of ethyl 3- [2- (1-cyclohexenyl) phenyl] propanoate and ethyl 3- [2- (2- (E) -tert-butyldimethylsilyloxy-ethenyl) phenyl] propanoate, respectively. The catalytic reaction of (E) -Methyl 4-oxa-6- ((Z) -2-propynylidene) undec-2-en-7-ynoate proceeds at 50 ﾟC to give benzoisodehydrofurane (E-form) as a sole product in 65% yield even without slow addition technique. The intervention of a vinylidene-rhodium and a 1,4-organorhodium diradical is proposed for intermediates of this catalytic reaction.

过渡金属可以充当就业的环磁瘤化的触发因素。在存在ET_3N和5 mol％[RHCl（I-PR_3P）_2]的情况下，催化异步就业的反应产生芳族碳氢化合物。类似于启示赛的环境反应通过乙烯基 - rHodiumn和1,4-核心hodium diradical进行的。在ET_3N和[RHCL（I-PR_3P）_2]的存在下，（Z）-3-二二烯-1,5-二烯慢慢地添加了注射泵在80 c中与苯基丙烯酸反应的乙烯在80 c中以3--（1-（1-（1-（1-（e）））在53％抗苯基苯基中，以53％的丙酸苯基苯基产生53％的苯基苯基。与其他烷基（例如乙基乙烯基酮和二甲基酸酯）的相似反应发生了，以中等至良好的产量给予相应的加合物。在所有情况下，都观察到了e-Olefinic产品的独家形成。还观察到（z）-1-氯己己-ExyC-3-ene-1,5-二烯和（Z）-1- tert-butyldim甲基二甲基二甲基甲基甲基氧基-5-5-ENE-5-3-3-3,7-二二烯的反应，也观察到了与乙基丙烯酸的枢纽的串联串联C-C键反应形成与乙基丙烯酸的反应。苯基]丙酸和乙基3- [2-（2-（e） - 丁基二甲基甲甲基 - 乙基）苯基]苯基苯甲酸酯。 （E） - 甲基4-oxa-6-（（（（Z）-2-丙基尼利））UNDEC-2-EN-7-YNOATE在50℃下进行的催化反应以65％的产量为唯一的产物，即使没有缓慢的添加技术，也以65％的产量为苯并二异硫代硫磺烷（E-e-form）进行催化反应。乙烯基rHodium和1,4-核桃diradical的干预是针对这种催化反应的中间体的。