Development of dehydrogenation reaction using palladium catalyst and ethylene system

钯催化剂与乙烯体系脱氢反应的进展

• 批准号: 13554022
• 负责人: HAYASHI Masahiko
• 金额: $ 5.57万
• 依托单位: Kobe University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13554022/
• 关键词: palladium catalyst; oxidative aromatization; heterocyclic compound; activated carbon; envirornmentally friendly reaction; ヘテロ環; パラジウム; 脱水素反応; 酸化反応; ピペリジン; ピラゾール; 複素環化合物; 芳香族化; 環境調和型反応

Recently reported oxidation process of alcohols using molecular oxygen as an oxidizing agent in the presence of catalytic amount of transition metals such as copper, ruthenium, and palladium compounds will be reviewed. Oxidation of alcohols based on hydrogen transfer reaction between alcohols and simple olefins such as ethylene is also described. That is, some benzylic and allylic alcohols can be converted into the corresponding carbonyl compounds using a catalytic amount of palladium on activated carbon (Pd-C) under ethylene atmosphere. The combination of Pd(OAc)2 and vinyl acetate also works efficiently. Selective oxidation of hydroxy groups on carbohydrates (D-glycals) and steroids as well as simpler systems has been achieved. Oxidative aromatization reaction has been also realized by Pd-C/acetic acid/02 system. 1,3,5-Trisubstituted pyrazolines and Hantzsch 1,4-dihydropyridines were converted into the corresponding pyrazoles and pyridines effectively by the treatment of a catalytic amount of Pd/C in acetic acid under oxygen atmosphere. Direct synthesis of 2-arylbenzoxazoles from 2-aminophenols and aldehydes was achieved in the presence of activated carbon (Darco KB) under oxygen atmosphere. These environmentally benign oxidation methods have potentialities to replace the conventional stoichiometric chromium and other metal oxidizing agents.

本文综述了近年来在过渡金属铜、钌、钯等催化剂存在下，以分子氧为氧化剂的醇类氧化反应的研究进展。还描述了基于醇和简单烯烃如乙烯之间的氢转移反应的醇的氧化。也就是说，在乙烯气氛下，使用催化量的钯/活性炭（Pd-C）可以将一些苄型和烯丙型醇转化为相应的羰基化合物。Pd（0Ac）2和乙酸乙烯酯的组合也有效地起作用。已经实现了碳水化合物（D-糖）和类固醇上的羟基的选择性氧化以及更简单的系统。Pd-C/乙酸/O2体系也实现了氧化芳构化反应。1，3，5-三取代吡唑啉和Hantzsch 1，4-二氢吡啶通过催化量的Pd/C在乙酸中在氧气气氛下有效地转化为相应的吡唑和吡啶。以2-氨基苯酚和醛为原料，在活性炭（Darco KB）存在下，在氧气气氛下直接合成了2-芳基苯并恶唑。这些环境友好的氧化方法具有替代传统化学计量的铬和其他金属氧化剂的潜力。

项目成果

Y.Kawashita: "Direct and Practical Synthesis of 2-Arylbenzoxazoles Promoted by Activated Carbon"Org.Lett.. 5. 3713-3715 (2003)

Y.Kawashita：“活性炭促进的 2-芳基苯并恶唑的直接和实用合成”Org.Lett.. 5. 3713-3715 (2003)

W.J.Drury, N.Zimmermann, M.Keenan, M.Hayashi, S.Kaiser, R.Goddard, A.Pfaltz: "Synthesis of Versatile Chiral N, P Ligands Derived from Pyridine and Quinoline"Angew, Chem., Int.Ed.Eng.. 43. 70-74 (2004)

W.J.Drury、N.Zimmermann、M.Keenan、M.Hayashi、S.Kaiser、R.Goddard、A.Pfaltz：“从吡啶和喹啉衍生的多功能手性 N、P 配体的合成”Angew，Chem.，Int.Ed

K.Yoshimoto: "Tris(2,4,6-trimethoxyphenyl)phosphine(TTMPP) : A Novel catalyst for Selective deacetylation"Chemistry Letters. 934-935 (2001)

K.Yoshimoto：“三(2,4,6-三甲氧基苯基)膦(TTMPP)：一种用于选择性脱乙酰化的新型催化剂”化学快报。

W.J.Drury: "Synthesis of Versatile Chiral N,P Ligands Derived from Pyridine and Quinoline"Angew.Chem.Int.Ed.. 43. 70-74 (2004)

W.J.Drury：“吡啶和喹啉衍生的多功能手性 N,P 配体的合成”Angew.Chem.Int.Ed.. 43. 70-74 (2004)

M.Hayashi, K.Yoshimoto, N.Hirata, K.Tanaka, N.Oguni, K.Harada, A.Matsushita, Y.Kawachi, H.Sasaki: "Enantioselective Addition of Diketene to Aldehydes Promoted by Chiral Schiff Base-Titanium Alkoxide Complex. Application to Asymmetric Synthesis of Potentia

M.Hayashi、K.Yoshimoto、N.Hirata、K.Tanaka、N.Oguni、K.Harada、A.Matsushita、Y.Kawachi、H.Sasaki：“手性席夫碱-钛促进双烯酮与醛的对映选择性加成