Development of New Reactions with Organometallic Reagents Stable in

使用稳定的有机金属试剂开发新反应

• 批准号: 14078215
• 负责人: OSHIMA Koichiro
• 金额: $ 62.72万
• 依托单位: Kyoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14078215/
• 关键词: Aqueous Media; Nickel; Trialkylborane; Alkvlation; コバルト; 環境調和型反応; ラジカル; 環化反応; カップリング反応; ラジカル反応; ビニル化; アリル化; 有機インジウム化合物; 有機カリウム化合物; 金属アート錯体; グリニャール反応剤; アリル化反応; シンナミルエーテル; 不飽和アルデヒドアセタール; 塩化クロム; 環状化合物

The alkylation of aldehydes with organometallic reagents is one of the most important reactions in organic chemistry. Conventional alkylborane reagents do not react with aldehydes. We disclosed that nickel-catalyzed alkylation of aldehydes with trialkylboranes proceeds smoothly in the presence of a catalytic amount of η^2-ally1-1,2,3,4,5-pentamethy1-1,3-cyclopentadiene or an excess of cesium carbonate to afford the corresponding secondary alcohols. Trialkylboranes prepared from borane-dimethyl sulfide and terminal olefins via hydroboration as well as commercially available trialkylboranes could be employed for the reaction. The reaction would proceed via 12-coordinated nickel complexes with aldehydes as key intermediates. Interestingly, water enabled alkylation of aldehydes with trialkylboranes under nickel catalysis without additives.

醛与有机金属试剂的烷基化是有机化学中最重要的反应之一。常规的烷基硼烷试剂不与醛反应。我们发现，镍催化的醛与三烷基硼烷的烷基化反应在催化量的 η^2-ally1-1,2,3,4,5-五甲基1-1,3-环戊二烯或过量的碳酸铯存在下顺利进行，得到相应的仲醇。由硼烷-二甲硫醚和末端烯烃通过硼氢化制备的三烷基硼烷以及市售三烷基硼烷均可用于该反应。该反应将通过 12 配位镍配合物以醛作为关键中间体进行。有趣的是，在镍催化下，水可以在没有添加剂的情况下使醛与三烷基硼烷发生烷基化。

项目成果

Yousuke Ikeda: "Cobalt-Catalyzed Heck-Type Reaction of Alkyl Halides with Styrenes"J. Am. Chem. Soc.. 124・23. 6514-6515 (2002)

池田阳介：“钴催化的烷基卤化物与苯乙烯的反应”J. Am. Soc. 124・23 (2002)

Radical Allylation, vinylation, alkynilation and Phenylation

自由基烯丙基化、乙烯基化、炔基化和苯基化

• 发表时间: 2005
• 期刊: Synthesis (in press)
• 作者: Kazuaki Takami

Nickel-catalyzed alkylation of aldehydes with trialkylboranes.

• DOI: 10.1021/ol051917b
• 发表时间: 2005-09
• 期刊: Organic letters
• 影响因子: 5.2
• 作者: K. Hirano;H. Yorimitsu;K. Oshima

Satoshi Mikami: "Palladium-Catalyzed Coupling Reaction of Alkenylgalliums with Aryl Halides"Synlett. 7. 1137-1139 (2002)

Satoshi Mikami：“烯基镓与芳基卤化物的钯催化偶联反应”Synlett。

Hidenori Kinoshita: "Pd(0)-Catalyzed Reaction of Alkynes with Trifurylgermane and CO Provinding Acylgermanes : Hydrometalcarbonylation of Alkynes"J. Am. Chem. Soc.. 124・16. 4220-4221 (2002)

Hidenori Kinoshita：“Pd(0)-催化的炔烃与三呋喃基锗烷和CO的反应：炔烃的氢金属羰基化”J. Soc. 124・16。