Development of practical metal-catalyzed carbenoid reactions for environmentally benign chemistry
| Project/Area Number |
17590005
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Chemical pharmacy
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| Research Institution | University of Toyama |
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Principal Investigator |
YAKURA Takayuki University of Toyama, Graduate School of Medicine and Pharmaceutical Sciences, Associate Professor, 医学薬学研究部(薬学), 助教授 (70220126)
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| Project Period (FY) |
2005 – 2006
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2006: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 2005: ¥2,400,000 (Direct Cost: ¥2,400,000)
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| Keywords | 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 |
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| Research Abstract |
Stereoselective Synthesis of C3-C12 Dihydropyran Portion of Antitumor Laulimalide Using Copper-catalyzed Oxonium Ylide Formation-[2,3] Shift
Copper-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 Amination
Stereoselective 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-propanediol
Dirhodium(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 Steps
Enantioselective 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
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Report
(3 results)
Research Products
(13 results)
