Development of a Pd-catalyzed Selective synthetic Method for Polysubstituted Benzenes

Pd催化多取代苯选择性合成方法的开发

• 批准号: 13650909
• 负责人: TSUKADA Naofumi
• 金额: $ 2.24万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650909/
• 关键词: palladium; aromatics; alkyne; allylmetal complex; tosylate; catalysis; benzene; cyclopentenone; 一酸化炭素; アルケニル化; 1,4-ジエン; ジイン; テトラリン; インダン; トシル酸アリル; アリルアルコール

In this study, we developed a novel synthetic method for polysubstituted benzenes, which is based on the key reaction of alkynes with π-allylpalladium complexes.(1)While there is few reports on the insertion of alkynes into π-allylpalladium complexes, we found that the insertion proceeds smoothly if the complex has a weak ligand, and utilized it for catalysis. In the catalysis, the ligating ability of leaving groups on allylating agents is quite important. Using allyl tosylate as an allylating compound, the reaction proceeded effectively. In this reaction, penta-substituted benzenes were obtained form one molecule of allyl tosylate and two moleculae of internal alkynes in moderate to high yields. Using terminal, alkynes, trisubstituted benzenes were formed.(2)All results in this study are consistent with the mechanism that includes the insertion of alkynes into π-allylpalladium complexes as a key step.(3)The addition of p-toluenesulfonic anhydride made an employment of allylis alcohols possible. The fact increases the usability of the catalysis because allylic alcohols are cheaper and more available than other allylic compounds.(4)Being carried out under carbon monoxide atmosphere, the reaction afforded cyclopentenones instead of arenes. Using alkenes instead of alkynes, the allylic alkenylation of allylic compounds took place.

本研究基于炔与π-烯丙基钯配合物的关键反应，提出了一种合成多取代苯的新方法。(1)虽然目前关于炔插入π-烯基钯配合物的报道很少，但我们发现，如果配合物具有弱配体，则插入可以顺利进行，并利用它进行催化。在催化过程中，烯化剂上留下基团的结扎能力是非常重要的。使用戊酸烯丙酯作为烯丙化化合物，反应进行得很有效。在此反应中，以中高收率由1个甲基酸烯丙酯分子和2个内炔分子合成了五取代苯。在末端，形成了炔、三取代苯。(2)本研究结果均符合以炔插入π-烯丙基钯配合物为关键步骤的机理。(3)对甲苯磺酸酐的加入使烯丙醇的使用成为可能。这一事实增加了催化的可用性，因为烯丙醇比其他烯丙化合物更便宜，更容易获得。(4)该反应在一氧化碳气氛下进行，产生的是环戊烯酮，而不是芳烃。用烯烃代替炔烃，进行了烯丙基化合物的烯丙烯化反应。

项目成果

Shuichi Sugawara: "Palladium-Catalyzed 1,6- and 1.5-diyne-carbon monoxide reaction for preparation of alkylidenecyclopentenones and_-butenolides"Journal of Molecular Catalysis : Chemical. 195. 55-61 (2003)

Shuichi Sukawara：“用于制备亚烷基环戊烯酮和_-丁烯内酯的钯催化的 1,6-和 1,5-二炔-一氧化碳反应”《分子催化杂志：化学》。

Naofumi Tsukada: "Palladium-catalyzed allylic alkenylation of allylic alcohols with n-butyl acrylate"Chemical Communications. n/a. 2404-2405 (2003)

Naofumi Tsukada：“钯催化烯丙醇与丙烯酸正丁酯的烯丙基化”化学通讯。

Shuichi Sugawara, Kumiko Uemura, Naofumi Tsukada, Yoshio Inoue: "Palladium-catalyzed 1,6-1,5-diyne-carbon monoxide reaction for preparation of alkylidenecyclopentenones and -butenolides"Journal of Molecular Catalysis : Chemical. Vol.195. 55-61 (2003)

Shuichi Sugarara、Kumiko Uemura、Naofumi Tsukada、Yoshio Inoue：“钯催化的 1,6-1,5-二炔-一氧化碳反应，用于制备亚烷基环戊烯酮和丁烯内酯”分子催化杂志：化学。

Naofumi Tsukada: "Palladium-Catalyzed Benzannulation from Alkynes and Allylic Compounds"The Journal of Organic Chemistry. 68. 5961-5966 (2003)

Naofumi Tsukada：“钯催化的炔烃和烯丙基化合物的苯并环化”有机化学杂志。

Naofumi Tsukada: "Palladium-Catalyzed Allylic Alkenylation of Allylic Alcohols with n-Butyl Acrylate"Chemical Communications. 2404-2405 (2003)

Naofumi Tsukada：“钯催化烯丙醇与丙烯酸正丁酯的烯丙基化”化学通讯。