课题基金 / 基金详情

Development of Electrophilic and Enantioselective Fluorinating Agents based on Fine Chemisty Design

Development of Electrophilic and Enantioselective Fluorinating Agents based on Fine Chemisty Design
基于精细化学设计的亲电和对映选择性氟化剂的开发
批准号:
07807193
负责人:
TAKEUCHI Yoshio
金额:
$1.28万
依托单位国家:
日本
项目类别:
Grant-in-Aid for Scientific Research (C)
财政年份:
1995
资助国家:
日本
项目状态:
已结题
起止时间:
1995 至 1996

项目摘要

项目成果

TAKEUCHI Yoshio的其他基金

相似基金

相关文献

中文摘要
翻译
1)(S)-缬氨酸和(S)-苯甘氨酸分别转化为4-取代的2-恶唑烷酮和2-噻唑烷酮。2)以Saccarin为原料,用两种烷基金属试剂反应,合成了3,3-二取代2,3-二氢苯并[1,2-d]异噻唑1,1-二氧化物。这些化合物用10-(+)-樟脑磺酰氯处理,得到非对映异构体,将其分离。将每种非对映异构体水解,得到(R)-或(S)-N-H衍生物。(R)-3-甲基-3-环己基衍生物(1)用氟气氟化,成功地得到了相应的(R)-N-F化合物(2)。(3)(S)-α-苯乙胺的N-甲苯磺酰基、N-甲磺酰基和N-三氟甲磺酰基衍生物的氟化,只得到了前两种化合物相应的N-F衍生物。然而,使用这些N-F衍生物的C-C1的立体选择性较低。4)尝试使用新的N-F试剂2对2-甲基-1-四氢萘酮(3)、2-苄基-1-四氢萘酮和2-氧代-环戊烷羧酸乙酯进行C-氟化。5)对化合物1、1的磺酰基衍生物、化合物2进行了X-射线单晶衍射分析。基于这些化合物氮原子周围的立体化学,从机理的角度研究了缩合反应的立体选择性。
英文摘要
1) (S)-Valine and (S)-phenylglycine were converted into 4-substituted 2-oxazolidinone and 2-thiazolidinone, respectively. Attempted fluorination of these compounds gave N-fluoro derivative only for the former compound.2) Saccarin was treated with two kinds of alkyl metal reagents to produce 3, 3-disubstituted 2, 3-dihydrobenzo [1, 2-d] isothiazole 1, 1-dioxides. These compounds were treated with 10-(+) - champhorsulfonyl chloride to give diastereomers, which were separated. Each diastereomer was hydrolyzed to give (R)- or (S) -N-H derivative. Fluorination of the (R) -3-methyl-3-cyclohexyl derivative (1) with fluorine gas produced the corresponding (R) -N-F compound (2) successfully.3) Attempted fluorination of N-tosyl, N-mesyl, and N-triflyl derivatives of (S) -alpha-phenethylamine yielded the corresponding N-F derivatives only for the two former compounds. However, the stereoselectivity of the C-fluorination employing these N-F derivatives was low.4) C-Fluorination of 2-methyl-1-tetralone (3), 2-benzyl-1-tetralone, and ethyl 2-oxo-cyclopentanecarboxylate was attempted employing the new N-F reagent 2. Bast result was obtained when 3 was treated with LDA/THF/50゚C - 0゚C and then allowed to react with 2 to afford the C-fluorinated product in 81% yield with ee of 80%.5) Compound 1, champhorsulfonyl derivative of 1, compound 2 were dubjected to X-ray crystallographic analyzes. Based on the stereochemistry around the nitrogen atoms of these compounds, stereoselectivity of the fluorination reaction was investigated form mechanistic viewpoint.
期刊论文(5)
专著(0)
科研奖励(0)
会议论文
H.Kakuda,T.Suzuki,Y.Takeuchi,M.Shiro: "X-Ray crystallographic structure determination of some unique chiral sultam derivatives" Chem.Commun.1977. 85-86 (1997)
H.Kakuda,T.Suzuki,Y.Takeuchi,M.Shiro:“一些独特的手性磺内酰胺衍生物的 X 射线晶体结构测定”Chem.Commun.1977。
DOI: --
发表时间:
期刊:
影响因子: --
作者: []
通讯作者:
H. Kakuda, T. Suzuki, Y. Takeuchi, M. Shiro: "X-Ray crystallographic structure determination of some unique chiral saltam derivatives" Chem. Commun.1997. 85-86 (1997)
H. Kakuda、T. Suzuki、Y. Takeuchi、M. Shiro:“一些独特的手性 saltam 衍生物的 X 射线晶体结构测定” Chem。
DOI: --
发表时间:
期刊:
影响因子: --
作者: []
通讯作者:
H.Kakuda, T.Suzuki, Y.Takeuchi, M.Shiro: "X-ray crystallographic structure determination of some unique chiral sultam derivatives" Chem. Commun.1997. 85-86 (1997)
H.Kakuda、T.Suzuki、Y.Takeuchi、M.Shiro:“一些独特的手性磺内酰胺衍生物的 X 射线晶体结构测定” Chem。
DOI: --
发表时间:
期刊:
影响因子: --
作者: []
通讯作者:
Y.Takeuchi, A.Satoh, T.Suzuki, A.Kameda, M.Dohrin, T.Satoh, T.Koizumi, K.L.Kirk: "Enantioselective Fluorination of Organic Molecules. 1. Synthetic studies of the Agents for Electrophilic, Enantioselective Fluorination of Carbanions" Chem. Pharm. Bull.45.
Y.Takeuchi、A.Satoh、T.Suzuki、A.Kameda、M.Dohrin、T.Satoh、T.Koizumi、K.L.Kirk:“有机分子的对映选择性氟化。1.亲电、对映选择性氟化试剂的合成研究
DOI: --
发表时间:
期刊:
影响因子: --
作者: []
通讯作者:
Design & Synthesis of Novel Enantioselctive Fluorinationg Agents
Efficient preparation of a highly versatile chiral derivatizing agent, CFTA, for determination of absolute configurations.
Novel Fluorinated Bioorganic Molecules for the 21st Century
  • 批准号:
    09044277
  • 项目类别:
    Grant-in-Aid for international Scientific Research
  • 资助金额:
    $4.1万
  • 财政年份:
    1997
  • 负责人:
    TAKEUCHI Yoshio
  • 依托单位:
Synthesis and Utilization of Fluorine-containing Chiral Building Blocks for Development of the New Type of Drugs
海外基金