Efficient and Selective Formation of Phenylacetic Acids from Diketene

从双烯酮高效选择性地形成苯乙酸

• 批准号: 24655087
• 负责人: KIMURA Masanari
• 金额: $ 2.66万
• 依托单位: Nagasaki University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Challenging Exploratory Research
• 财政年份: 2012
• 资助国家: 日本
• 起止时间: 2012-04-01 至 2014-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-24655087/
• 关键词: ニッケル; 有機亜鉛; 有機アルミニウム; アルキン; ジケテン; 環化付加; ニッケル触媒; ジメチル亜鉛; フェニル酢酸; 環化付加反応

In the presence of Ni catalyst, three components of diketene, alkyne, and Me2Zn combine smoothly to provide 3-methylene-4-hexenoic acids in excellent yields. Furthermore, under similar catalytic conditions, Et2Al(OEt) promotes [2+2+2] cycloaddition reactions with diketene and 2 equivalents of alkyne to give rise to the substituted phenylacetic acids. More interestingly, in the presence of Et2Al(OEt) and phosphine ligand, symmetrical phenyl acetic acids are constructed via the formal [2+2+1+1] cycloaddition reactions with diketene and 2 equivalents of alkyne accompanying the cleavage reaction of methylene C=C double bond of diketene.This is the first example of the selective formation of unsaturated carboxylic acids and phenylacetic acids from diketene involving oxanickelacycles. The reaction presented here might be a powerful tool in the expedient synthesis of the physiologically active molecules, such as isoprenoid acids and non-steroidal anti-inflammatory drugs (NSAIDs).

在Ni催化剂的作用下，二烯酮、炔和Me2Zn三种组分顺利结合，得到了收率高的3-亚甲基-4-己烯酸。此外，在类似的催化条件下，Et2Al（OEt）与二烯酮和2个当量炔催化[2+2+2]环加成反应生成取代苯乙酸。更有趣的是，在Et2Al（OEt）和膦配体存在下，通过与二烯酮和2个当量炔的形式[2+2+1+1]环加成反应，并伴随二烯酮的亚甲基C=C双键的裂解反应，构建对称苯乙酸。这是涉及氧环的二烯酮选择性形成不饱和羧酸和苯乙酸的第一个例子。该反应可能是合成生理活性分子的有力工具，如异戊二烯酸和非甾体抗炎药（NSAIDs）。

项目成果

Regioselective C-H Arylation of Pyridine Derivatives Promoted by Iron Catalyst

铁催化剂促进吡啶衍生物的区域选择性 C-H 芳基化

• 发表时间: 2013
• 作者: Y. Akioka;G. Onodera;M. Kimura
• 通讯作者: M. Kimura

Ni-Catalyzed Multi-component Coupling Reaction of Norbornene, Dimethylzinc, Butadiene, and Aldimine

镍催化降冰片烯、二甲基锌、丁二烯和醛亚胺的多组分偶联反应

• 发表时间: 2012
• 期刊: Heterocycles
• 影响因子: 0.6
• 作者: T. Nakamura;T. Mori;M. Togawa;M. Kimura.
• 通讯作者: M. Kimura.

Ni-Catalyzed Selective Formation of Unsaturated Carboxylic Acid and Phenyl Acetic Acid Derivatives from Diketene and Alkyne

镍催化双烯酮和炔烃选择性生成不饱和羧酸和苯乙酸衍生物

• 发表时间: 2013
• 作者: T. Mori;Y. Akioka;H. Kawahara;G. Onodera;M. Kimura
• 通讯作者: M. Kimura

Ni-Catalyzed selective formation of unsaturated carboxylic acid and phenylacetic acid from diketene

Ni催化双乙烯酮选择性生成不饱和羧酸和苯乙酸

• 发表时间: 2013
• 作者: T. Mori;G. Onodera;M. Kimura
• 通讯作者: M. Kimura

生物有機化学研究室

生物有机化学实验室