Development of practical metal-catalyzed carbenoid reactions for environmentally benign chemistry

开发用于环境友好化学的实用金属催化类胡萝卜素反应

• 批准号: 17590005
• 负责人: YAKURA Takayuki
• 金额: $ 2.24万
• 依托单位: University of Toyama
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2005
• 资助国家: 日本
• 起止时间: 2005 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-17590005/
• 关键词: metal-catalyzed reaction; oxonium ylide; [2,3]sigmatropic rearrangement; C-H amination; diazoketone; carbamate; Rh(II)触媒C-Hアミノ化; conagenin; α-メチルアミノ酸; pachastrissamine; 免疫調節薬; スフィンゴシン関連物質; laulimalide; 抗腫瘍活性

Stereoselective Synthesis of C3-C12 Dihydropyran Portion of Antitumor Laulimalide Using Copper-catalyzed Oxonium Ylide Formation-[2,3] ShiftCopper-catalyzed oxonium ylide formation-[2,3] shift of (5S,7R)-5-allyloxy-1-diazo-8-(p-methoxybenzyloxy)-7-methyl-2-octanone proceeded in tetrahydrofuran-dichloromethane (4:1) under reflux with an excellent stereoselectivity (97:3) to give (2R,6S)-2-allyl-6-[(2R)-3-(p-methoxybenzyloxy)-2-methylpropyl]-3-dihydropyranone (2) as a major isomer in 82% yield. The resultant pyranone was converted to the key intermediate of the Mulzer's laulimalide synthesis and its derivatives.Synthesis of an Immunomodulator (+)-Conagenin and Its Analogs using Dirhodium(II)-catalyzed C-H AminationStereoselective synthesis of an immunomodulator (+)-conagenin was achieved. Both amine and carboxylic acid moieties were prepared from commercially available optically active methyl 3-hydroxy-2-methylpropanoate using dirhodium(II)-catalyzed C-H amination and chelation-controlle … More d reductions as key steps. In addition, demethyl analogs of conagenin were synthesized using similar procedures.Dirhodium(II)-catalyzed C-H Amination Reaction of (S)-3-(tert-Butyldimethylsilyloxy)-2-methylpropyl Carbamate : A Facile Preparation of Optically Active Monoprotected 2-Amino-2-methyl-1,3-propanediolDirhodium(II)-catalyzed C-H amination reaction of (S)-3-(tert-butyldimethylsilyloxy)-2-methylpropyl carbamate, which was easily prepared from methyl (S)-2-methyl-3-hydroxypropanoate, proceeded more smoothly than those of their 2-(methoxycarbonyl)propyl derivative to give the corresponding oxazolidinone in excellent yield. The resulting oxazolidinone was converted efficiently into both (R)-monoprotected and (S)-monoprotected 2-amino-2-methyl-1,3-propanediols.Enantioselective Synthesis of Pachastrissamine (Jaspin B) using Dirhodium(II)-catalyzed C-H Amination and Asymmetric Dihydroxylation as Key StepsEnantioselective total synthesis of anhydrophytosphingosine pachastrissamine (jaspin B) was achieved using the Sharpless asymmetric dihydroxylation and dirhodium(II)-catalyzed C-H amination as key steps. Less

使用铜催化的氧鎓叶立德形成-[2,3]位移立体选择性合成抗肿瘤药月立马利特的C3-C12二氢吡喃部分铜催化的氧鎓叶立德形成-[2,3]位移 (5S,7R)-5-烯丙氧基-1-重氮基-8-(对甲氧基苄氧基)-7-甲基-2-辛酮在四氢呋喃-二氯甲烷(4:1)回流下进行，具有优异的立体选择性(97:3)，得到 (2R,6S)-2-烯丙基-6-[(2R)-3-(对甲氧基苄氧基)-2-甲基丙基]-3-二氢吡喃酮(2)作为主要异构体，产率82%。所得吡喃酮转化为Mulzer's laulimalide合成及其衍生物的关键中间体。 二铑(II)催化C-H胺化合成免疫调节剂(+)-刀豆蛋白及其类似物实现了免疫调节剂(+)-刀豆蛋白的立体选择性合成。胺和羧酸部分都是由市售的光学活性 3-羟基-2-甲基丙酸甲酯制备而成，使用二铑 (II) 催化的 C-H 胺化和螯合控制的 d 还原作为关键步骤。此外，使用类似的程序合成了conagenin的去甲基类似物。二铑(II)催化的(S)-3-(叔丁基二甲基硅氧基)-2-甲基丙基氨基甲酸酯的C-H胺化反应：光学活性单保护的简便制备 2-氨基-2-甲基-1,3-丙二醇二铑(II)催化的(S)-3-(叔丁基二甲基硅氧基)-2-甲基丙基氨基甲酸酯的C-H胺化反应比它们的反应更顺利，该反应很容易由(S)-2-甲基-3-羟基丙酸甲酯制备 2-(甲氧基羰基)丙基衍生物以优异的收率得到相应的恶唑烷酮。所得恶唑烷酮可有效转化为 (R)-单保护和 (S)-单保护 2-氨基-2-甲基-1,3-丙二醇。使用二铑 (II) 催化的 C-H 胺化和不对称二羟基化作为关键步骤对映选择性合成 Pachastrissamine (Jaspin B) 使用 Sharpless 不对称二羟基化和二铑 (II) 催化的 C-H 胺化作为关键步骤，获得了脱水植物鞘氨醇 pachastrissamine (jaspin B)。较少的