(1S,6R,7S,8R,8aR)-1,7-Diacetoxy-8-(benzyloxy)-6-fluorooctahydro-5-indolizidin-5-one | 131635-71-7

• 分子结构分类: 有机化合物
• 英文名称: (1S,6R,7S,8R,8aR)-1,7-Diacetoxy-8-(benzyloxy)-6-fluorooctahydro-5-indolizidin-5-one
• 英文别名: [(1S,6R,7S,8R,8aR)-7-acetyloxy-6-fluoro-5-oxo-8-phenylmethoxy-2,3,6,7,8,8a-hexahydro-1H-indolizin-1-yl] acetate
• CAS: 131635-71-7
• 化学式: C₁₉H₂₂FNO₆
• 分子量: 379.385
• InChiKey: VDKUPAARTZUQBE-YYWYGQEZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  27
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  82.1
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (1S,6R,7S,8R,8aR)-1,7-Diacetoxy-8-(benzyloxy)-6-fluorooctahydro-5-indolizidin-5-one 在 palladium on activated charcoal 盐酸 、 甲酸 、 dimethyl sulfide borane 、 氢气 作用下， 以 甲醇 为溶剂， 反应 16.0h， 生成 (+)-6-deoxy-6-fluorocastanospermine
  参考文献：
  名称：

  酒石酸衍生的新型光学纯乙烯酮当量在（+）-6-脱氧金刚烷胺和（+）-6-脱氧-6-氟金刚烷胺的全部不对称合成中的应用

  摘要：

  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）。

  DOI：

  10.1039/c39900001070
• 作为产物：
  描述：

  (5S,6S,7S)-7-Acetoxy-5-(benzyloxy)-1-azabicyclo<4.3.0>non-3-en-2-one 在 吡啶 、 甲醇 、 4-二甲氨基吡啶 、 氯化亚砜 、 dimethyl sulfide borane 、 2-(tert-butylimino)-2-(diethylamino)-1,3-dimethylperhydro-1,3,2-diazaphosphorine on polystyrene 、 溴 、 silver(I) acetate 、 potassium carbonate 、 triethylamine tris(hydrogen fluoride) 作用下， 反应 21.5h， 生成 (1S,6R,7S,8R,8aR)-1,7-Diacetoxy-8-(benzyloxy)-6-fluorooctahydro-5-indolizidin-5-one
  参考文献：
  名称：

  Total, asymmetric synthesis of (+)-castanospermine, (+)-6-deoxycastanospermine, and (+)-6-deoxy-6-fluorocastanospermine

  摘要：

  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.

  DOI：

  10.1021/jo00006a031

文献信息

• 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：——