Development of New Transition Metal-Catalyzed Systems under Oxygen

氧气下新型过渡金属催化体系的开发

• 批准号: 11450345
• 负责人: UEMURA Sakae
• 金额: $ 9.47万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11450345/
• 关键词: Palladium (II) Acetate; Oxygen; Alcohol Oxidation; Alkene Oxidation; Hydrotalcite; Fluorous Biphase System; tert-Cyclobutanols; Clay Catalyst; パラジウム(II)-ハイドロタルサイト; アリル位アルコール; ピリジン; 酸素酸化; 触媒反応

We disclosed a new palladium (II) catalytic system for oxidation of alcohols. The system consisted of a catalytic amount of Pd (OAc)_2, atmospheric pressure of oxygen as an oxidant, and an organic base such as pyridine in toluene. The finding is as follows : 1) a selective oxidation of primary and secondary alcohols to the corresponding aldehydes and ketones, respectively, 2) oxidation of tertiary cyclobutanols to various organic compounds such as β, γ-unsaturated ketones, cyclopentanone derivatives, tetralone derivatives, and cyclopropyl ketones depending on the kind of substituents on the cyclobutane ring. We also developed a new solid catalyst, palladium (II) hydrotalcite, by the reaction of Pd (OAc)_2 with a basic clay hydrotalcite. This solid catalyst is reusable and also has a characteristic feature in oxidation of unsaturated allylic alcohols such as geraniol and nerol to the corresponding aldehydes without any isomerization at the double bond. All these new findings have been reported in scientific journals of Japan, UK and USA.

我们公开了一种用于醇氧化的新的钯（II）催化体系。该体系由催化量的Pd（OAc）_2、常压氧气氧化剂和有机碱如吡啶在甲苯中组成。结果表明：1）伯醇和仲醇分别选择性氧化为相应的醛和酮; 2）叔环丁醇氧化为各种有机化合物，如β，γ-不饱和酮、环戊酮衍生物、四氢萘酮衍生物和环丙基酮，这取决于环丁烷环上取代基的种类。我们还通过Pd（OAc）_2与一种碱性粘土水滑石的反应，开发了一种新的固体催化剂--钯（II）水滑石。该固体催化剂可重复使用，并且在不饱和烯丙醇如香叶醇和橙花醇氧化成相应的醛而在双键处没有任何异构化方面也具有特征性特征。所有这些新发现都已在日本、英国和美国的科学杂志上发表。

项目成果

Takahiro Nishimura et al.: "Oxidative Transformation of tert-Cyclobutanols by Palladium Catalysts under Oxygen Atmosphere"J.Org.Chem.. 66・4. 1455-1465 (2001)

Takahiro Nishimura等：“氧气气氛下钯催化剂对叔环丁醇的氧化转化”J.Org.Chem.. 1455-1465 (2001)。

西村貴洋: "Palladinm(II)-Catalyzed Oxidative Ring Clearage of tert-Cyclobutanols"J. Am. Chem. Soc.. 121. 2645-2646 (1999)

Takahiro Nishimura：“叔环丁醇的钯 (II) 催化氧化环清除”J. Am. Soc.. 121. 2645-2646 (1999)

Takahiro Nishimura et al: "Palladium (II)-Supported Hydrotalcite as a Catalyst for Selective Oxidation of Alcohols using Molecular Oxygen"Chem.Commun.. 1245-1246 (2000)

Takahiro Nishimura 等人：“钯 (II) 支持的水滑石作为使用分子氧选择性氧化醇的催化剂”Chem.Commun.1245-1246 (2000)

Takahiro Nishimura et al: "Palladium (II)-Catalyzed Oxidation of Alcohols to Aldehydes and Ketones by Molecular Oxygen"J.Org.Chem.. 64 18. 6750-6755 (1999)

Takahiro Nishimura 等人：“通过分子氧钯 (II) 催化醇氧化成醛和酮”J.Org.Chem.. 64 18. 6750-6755 (1999)

西村貴洋: "Palladium (II)-Catalyzed Oxidation of Alcohols to Aldehydes and Ketones"J. Org. Chem.. 64. 6750-6755 (1999)

Takahiro Nishimura：“钯 (II) 催化醇氧化成醛和酮”J. Org. 64. 6750-6755 (1999)