| 123190-64-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 123190-64-7；123284-49-1；131722-83-3；131722-91-3
• 化学式: C₁₇H₂₀ClNO₅
• 分子量: 353.803
• InChiKey: JXGYNRXXNPPQLJ-IBCJJDNGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  24.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  65.07
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  在 palladium on activated charcoal 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 、 氢气 、 溴 、 silver(I) acetate 、 potassium carbonate 作用下， 以 四氢呋喃 、 乙醇 、 水 为溶剂， 20.0~130.0 ℃ 、101.33 kPa 条件下， 反应 172.5h， 生成 栗精胺
  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