(+)-6-deoxy-6-fluorocastanospermine | 131635-62-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚里西啶
• 英文名称: (+)-6-deoxy-6-fluorocastanospermine
• 英文别名: 6-deoxy-6-fluorolcastenospermine；6-Deoxy-6-fluorocastanospermine；(1S,6S,7S,8R,8aR)-6-fluoro-1,2,3,5,6,7,8,8a-octahydroindolizine-1,7,8-triol
• CAS: 131635-62-6
• 化学式: C₈H₁₄FNO₃
• 分子量: 191.202
• InChiKey: JOYRDAUHIQFEBO-TVNFTVLESA-N

物化性质

• 熔点：
  142-143 °C
• 沸点：
  349.7±42.0 °C(Predicted)
• 密度：
  1.45±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.2
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  63.9
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  栗精胺 在 palladium on activated charcoal 吡啶 、 二乙胺基三氟化硫 、 氨 、 氢气 、 三丁基氧化锡 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 乙酸乙酯 为溶剂， 25.0 ℃ 、413.69 kPa 条件下， 反应 7.0h， 生成 (+)-6-deoxy-6-fluorocastanospermine
  参考文献：
  名称：

  粟精胺的化学，第一部分：C-6的合成修饰

  摘要：

  概述了粟精胺的选择性功能化的方法学，该方法学允许合成许多在C-6处选择性修饰的类似物。还从粟精胺合成了Australine和一些australine类似物。

  DOI：

  10.1016/s0040-4020(01)85075-4

文献信息

• Application of new optically pure ketene equivalents derived from tartaric acids to the total, asymmetric syntheses of (+)-6-deoxycastanospermine and (+)-6-deoxy-6-fluorocastanospermine
  作者：Jean-Louis Reymond、Pierre Vogel

  DOI：10.1039/c39900001070

  日期：——

  5S, 7S)-3-ethyl-2-oxo-6, 8-dioxa-3-azabicyclo[3.2.1]octane-7-carboxylic acid (8) whose 1-cyanovinyl ester (10) added to furan to give, after two recrystallizations, an optically pure 7-oxabicyclo[2.2.1]hept-5-en-2-yl derivative (11) that was converted into (+)-6-deoxycastanospermine (+)-(2) and (+)-6-deoxy-6-fluorocastanospermine (+)-(3).

  二-O-乙酰基-（S，S）-酒石酸酐与二乙缩醛的缩合。N-乙基氨基乙醛得到（1 S，5 S，7 S）-3-乙基-2-氧代-6，8-二氧杂-3-氮杂双环[3.2.1]辛烷-7-羧酸（8），其1-氰基乙烯基将酯（10）添加到呋喃中，经过两次重结晶后，得到光学纯的7-氧杂双环[2.2.1]庚-5-烯-2-基衍生物（11），将其转变为（+）-6-脱氧castanospermine（ +）-（2）和（+）-6-脱氧-6-氟castanospermine（+）-（3）。
• Total, asymmetric synthesis of (+)-castanospermine, (+)-6-deoxycastanospermine, and (+)-6-deoxy-6-fluorocastanospermine
  作者：Jean Louis Reymond、A. Alan Pinkerton、Pierre Vogel

  DOI：10.1021/jo00006a031

  日期：1991.3

  Bromination of the dibenzyl acetal of (-)-(1S,4S)-7-oxabicyclo[2.2.1]hept-5-en-2-one ((-)-5) led to (+)-(1S,5S,6S,7S)-6-endo-(benzyloxy)-5-exo-bromo-7-oxabicyclo[2.2.1]heptan-2-one (25). Baeyer-Villiger oxidation of 25 gave 2-O-benzyl-3-bromo-3,5-dideoxy-beta-L-arabino-hexofuranosidurono-6,1-lactone (26). Methanolysis of 26 afforded the corresponding methyl (methyl alpha-beta-L-arabinofuranosid)uronates (27 + 28). The alpha anomer 27 was reduced with DIBAH into methyl 2-O-benzyl-3-bromo-3,5-dideoxy-beta-L-arabino-hexofuranoside (29). Mesylation of the primary alcohol, followed by treatment with NH3 gave methyl 2-O-benzyl-3,5-6-trideoxy-3,6-imino-beta-L-lyxo-hexofuranoside (32). Acetylation of the amine with ClCH2COCl, acetolysis of the methyl furanoside followed by Arbuzov condensation with (EtO)3P, and then intramolecular Horner-Emmons reaction led to (5S,6S,7S)-7-hydroxy-5-(benzyloxy)-1-azabicyclo[4.3.0]non-3-en-2-one (37). Base-catalyzed hydrolysis of the corresponding epoxide 43 ((1S,6S,7S,8R,8aS)-8-(benzyloxy)-6,7-epoxy-1-hydroxyoctahydroindolizidin-5-one) followed by reduction of the lactam and deprotection of the alcoholic functions afforded (+)-castanospermine ((+)-1). The conversion of (-)-5 into (+)-1 was highly stereoselective, requiring the isolation of 10 synthetic intermediates and with an overall yield of 15.2%. Reduction of 43 with BH3.Me2S or its treatment with HF.Et3N allowed one to prepare readily (+)-6-deoxycastanospermine ((+)-2 and 6-deoxy-6-fluorocastanospermine ((+)-3). The crystal structure of (+)-3 is also reported.
• REYMOND, JEAN-LOUIS;VOGEL, PIERRE, J. CHEM. SOC. CHEM. COMMUN.,(1990) N6, C. 1070-1072
  作者：REYMOND, JEAN-LOUIS、VOGEL, PIERRE

  DOI：——

  日期：——
• REYMOND, JEAN-LOUIS;PINKERTON, A. ALAN;VOGEL, PIERRE, J. ORG. CHEM., 56,(1991) N, C. 2128-2135
  作者：REYMOND, JEAN-LOUIS、PINKERTON, A. ALAN、VOGEL, PIERRE

  DOI：——

  日期：——
• The chemistry of castanospermine, part I: synthetic modifications at C-6
  作者：Richard H. Furneaux、Graeme J. Gainsford、Jennifer M. Manson、Peter C. Tyler

  DOI：10.1016/s0040-4020(01)85075-4

  日期：1994.2

  Methodology for the selective functionalisation of castanospermine is outlined which has allowed the synthesis of a number of analogues selectively modified at C-6. Australine and some australine analogues have also been synthesized from castanospermine.

  概述了粟精胺的选择性功能化的方法学，该方法学允许合成许多在C-6处选择性修饰的类似物。还从粟精胺合成了Australine和一些australine类似物。