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.

我们开发了新的C-C键形成方法，其中包括作为关键中间体的新型碲酸盐配合物。当乙烯基碲化物与有机锌化合物反应时，保持了乙烯基基团的几何构型，发生了Te-Zn交换反应。乙烯基锌化合物与卤代烷基化合物反应得到交叉偶联产物。在对过渡金属络合物的研究过程中，我们发现了一种新型的过渡金属络合物，它与格氏试剂联合使用，催化了烯烃和二烯的烷基化和硅基化反应。值得注意的是，在后期过渡金属催化反应中，脂肪族烷基卤化物和氯化硅的使用受到了极大的限制，它们在这些催化反应体系中得到了成功的应用。

项目成果

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。

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”。

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)。

寺尾潤: "Synthesis and Reaction of Vinylic Telurides"Phosphoruo Sulphur and Silicon. 136.137&138. 637-640 (1998)

Jun Terao：“乙烯基碲化物的合成和反应”磷硫和硅 136.137&138 (1998)。