Generation and Reaction of Hyperralent Hetero-atom

高惰性杂原子的产生与反应

• 批准号: 10450335
• 负责人: KAMBE Nobuaki
• 金额: $ 8.64万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10450335/
• 关键词: ate complex; telurium compaund; zirconium catalyst; litanium catalyst; alkylation; silylation; carbodiimide; カルボジイシド; ヘテロ原子; 高原子価状態; ハイパーバレント活性種; カルボニルリチウム; シリル化反応; アルキル化反応

We have developed new C-C bond formation methodology, which includes novel type of tellurium ate complexes as key intermediates. When the reaction of vinylic telluride with organic zinc compound was carried out, Te-Zn exchange reaction took place with retention of the geometry of vinyl moiety. The treatment of the vinylic zinc compounds with alkyl halide gave the cross coupling product. During the course of our study on the ate complex involving transition-metal complex, we have found the novel titanocene or zirconocene catalyzed alkylation and silylation of olefin and diene with the combined use of Grignard reagent. It should be noted that aliphatic alkyl halide and silyl chloride, whose usage are significantly limited in the late transition-metal catalyzed reaction were successfully employed in these catalytic reaction system.

我们已经开发了新的C-C键形成方法，其中包括新型的Tellurium Ate复合物作为关键中间体。当进行紫杉酸酯与有机锌化合物的反应时，随着乙烯基部分的几何形状的保留，Te-Zn交换反应发生。用烷基卤化物对藤蔓化合物的处理产生了交叉耦合产物。在涉及过渡金属复合物的ATE复合物的研究过程中，我们发现了新型的钛法或锆石催化的烷基化和烯烃和二烯的硅烷化，并与Grignard Reagent的综合使用。应该注意的是，在这些催化反应系统中成功使用了脂肪族烷基卤化物和甲硅烷基氯化物，它们在晚期过渡金属催化反应中的用法被显着限制。

项目成果

Shin-ichi Fujiwara, Nobuaki Kambe, Noboru Sonoda: "Synthesis and Reactions of Carbonyl Selenide and Isoselenocyanates in "Organoselenium Chemistry. A Practical Approach""Thomas G. Back (Ed.), Oxford University Press, New York. (1999)

Shin-ichi Fujiwara、Nobuaki Kambe、Noboru Sonoda：“有机硒化学中羰基硒化物和异硒氰酸酯的合成和反应”。

Jun Terao, Koyu Saito, Shinsuke Nii, Nobuaki Kambe, Noboru Sonoda: "Regioselective Double Alkylation of Styrenes with Alkyl Halides Using a Titanocene Catalyst"J. Am. Chem. Soc. 120 (45). 11822-11823 (1998)

Jun Terao、Koyu Saito、Shinsuke Nii、Nobuaki Kambe、Noboru Sonoda：“使用二茂钛催化剂对苯乙烯与烷基卤化物进行区域选择性双烷基化”J。

Shin-ichi Fujiwara, Takahiro Matsuya, Hajime Maeda, Tsutomu Shin-ike, Nobuaki Kambe, Noboru Sonoda: "Selenium-Assisted One-Pot Synthesis of Carbodiimides from Isocyanides and Primary Amines"Synlett. (1). 75-76 (1999)

Shin-ichi Fujiwara、Takahiro Matsuya、Hajime Maeda、Tsutomu Shin-ike、Nobuaki Kambe、Noboru Sonoda：“硒辅助异氰化物和伯胺一锅法合成碳二亚胺”Synlett。

寺尾 潤: "Regioselective Double Alkylation of Styrenes with Alkyl Halides Using a Titanocene Catalyst"J.Am.Chem.Soc.. 120(45). 11822-11823 (1998)

Jun Terao：“使用二茂钛催化剂对苯乙烯进行区域选择性双烷基化”J.Am.Chem.Soc. 120(45) (1998)。

藤原眞一: "A New Synthesis of Serenol Esters via Cabophilic Addition of Organocoppor Reagens to Carbonyl Selenides"J. Org. Chem.. 63(5). 1724-1726 (1998)

Shinichi Fujiwara：“通过有机铜试剂与羰基硒化物的亲热加成合成 Serenol 酯”J. Org. 1724-1726 (1998)。