Catalytic Asymetric Hydrogenation of Heteroaromatics

杂芳烃的催化不对称加氢

• 批准号: 11650891
• 负责人: KUWANO Ryoichi
• 金额: $ 2.3万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 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/grant/KAKENHI-PROJECT-11650891/
• 关键词: Catalytic Asymmetric Synthesis; Chiral Phosphine; Asymmetric Hydrogenation; Indoline; Heteroaromatics; Indole; Rhodium; 光学活性ピラジン; 複素芳香環; 水素化; 光学活性化合物

1. Catalytic Hydrogenation of Heteroaromatic Compounds using Transition Metal ComplexWe found that rhodium complex generated from Rh (acac)(cod) and triphenylphosphine exhibited high catalytic activity for hydrogenation of indoles. The rhodium catalyst was also effective in hydrogenation of other 5-membered heteroaromatic compounds.2. Catalytic Asymmetric Hydrogenation of 2-Substituted IndolesThe hydrogenation of N-acetyl-2-butylindole proceeded in the presence of cataionic (S, S)-(R,R)-PhTRAP-rhodium complex and cesium carbonate, giving (R)-N-acetyl-2-butylindoline with 94% ee in 92% isolated yield. This reaction is the first example of highly enantioselective hydrogenation of 5-membered heteroaromatic compounds. The chiral catalyst showed high enantioselectivity for the hydrogenation of other 2-substituted indoles (up to 95% ee).3. Catalytic Asymmetric Hydrogenation of 3-Substituted IndolesThe chiral PhTRAP-rhodium catalyst exhibited good enantioselectivity (86% ee) for the hydrogenation of N-acetyl-3-methylindole, but the reaction was accompanied by serious alcoholysis of N-acetyl group. p-Toluenesulfonyl group is the protective group on nitrogen of choice in asymmetric hydrogenation of 3-substituted indoles. The hydrogenation of 3-methyl-N-p-toluenesulfonylindole gave the corresponding indoline with 98% ee in 93% isolated yield.

1. 用过渡金属络合物催化杂芳香族化合物加氢我们发现由Rh (acac)（cod）和三苯基膦生成的铑络合物对吲哚的加氢具有较高的催化活性。铑催化剂对其他5元杂芳香族化合物的加氢反应也很有效。2-取代吲哚的催化不对称加氢在阳离子（S， S）-(R，R)- phrap -铑络合物和碳酸铯的存在下进行n -乙酰-2-丁啉的加氢，得到(R)- n -乙酰-2-丁啉，ee为94%，分离收率为92%。该反应是5元杂芳香族化合物高度对映选择性加氢的第一个例子。该手性催化剂对其他2-取代吲哚的加氢反应具有较高的对映选择性（可达95% ee）。催化3-取代吲哚的不对称加氢作用手性phtrap -铑催化剂对n -乙酰-3-甲基吲哚的加氢反应具有良好的对映选择性（86% ee），但反应同时伴有n -乙酰基的严重醇解。对甲苯磺酰基是3-取代吲哚不对称氢化反应中氮上选择的保护基团。3-甲基- n -对甲苯磺酰吲哚的加氢反应得到相应的吲哚，其ee为98%，分离收率为93%。

项目成果

R.Kuwano: "Hydrogenation of Five-Membered Heteroaromatic Compounds Catalyzed by Rhodium-Phosphine Complex"Chemistry Letters. (印刷中). (2000)

R. Kuwano：“铑-膦配合物催化的五元杂芳族化合物的氢化”化学快报（2000 年出版）。

Ryoichi Kuwano: "Asymmetric Hydrosilylation of Ketones Using Trans-Chelating Chiral Bisphosphine Ligands Bearing Primary Alkyl Substituents on Phosphorus Atoms"Bulletin of the Chemical Society of Japan. 73. 485-496 (2000)

Ryoichi Kuwano：“使用磷原子上带有伯烷基取代基的反式螯合手性双膦配体对酮进行不对称氢化硅烷化”日本化学会通报。

Ryoichi Kuwano: "Enantioselective Construction of Quaternary α-Carbon Centers on α-Amino Phosphonates via Catalytic Asymmetric Allylation"Organic Letters. 1. 837-839 (1999)

Ryoichi Kuwano：“通过催化不对称烯丙基化在 α-氨基磷酸酯上对映选择性构建季 α-碳中心”有机快报 1. 837-839 (1999)

Ryoichi Kuwano: "Hydrogenation of Five-Membered Heteroaromatic Compounds Catalyzed by a Rhodium-Phosphine Complex"Chemistry Letters. 428-429 (2000)

Ryoichi Kuwano：“铑-膦配合物催化的五元杂芳族化合物的氢化”化学快报。

Ryoichi Kuwano: "Asymmetric Aldol Reaction of 2-Cyanopropionates Catalyzed by a Trans-Chelating Chiral Diphosphine-Rhodium(I) Complex : Highly Enantioselective Construction of Quaternary Chiral Carbon Centers at α-Positions of Nitriles"Journal of Organome

Ryoichi Kuwano：“反式螯合手性二膦-铑(I)配合物催化的2-氰基丙酸酯的不对称羟醛反应：在腈的α位上高度对映选择性构建季手性碳中心”Journal of Organome