Methyl (Methyl 2-O-benzyl-3-bromo-3,5-dideoxy-α-L-arabinofuranosid)uronate | 131635-65-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Methyl (Methyl 2-O-benzyl-3-bromo-3,5-dideoxy-α-L-arabinofuranosid)uronate
• 英文别名: methyl 2-[(2S,3S,4S,5R)-3-bromo-5-methoxy-4-phenylmethoxyoxolan-2-yl]acetate
• CAS: 131635-65-9
• 化学式: C₁₅H₁₉BrO₅
• 分子量: 359.217
• InChiKey: YWDURRBBTQHBHK-SPWCGHHHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Methyl (Methyl 2-O-benzyl-3-bromo-3,5-dideoxy-α-L-arabinofuranosid)uronate 在 吡啶 、 ammonium hydroxide 、 二异丁基氢化铝 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 34.0h， 生成 Methyl 2-O-Benzyl-N-(chloroacetyl)-3,5,6-trideoxy-3,6-imino-β-L-lyxo-hexofuranoside
  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
• 作为产物：
  描述：

  (1S,5S,6S,7S)-6-bromo-7-phenylmethoxy-2,8-dioxabicyclo[3.2.1]octan-3-one 、 氯化亚砜 以82%的产率得到
  参考文献：
  名称：

  REYMOND, JEAN-LOUIS;PINKERTON, A. ALAN;VOGEL, PIERRE, J. ORG. CHEM., 56,(1991) N, C. 2128-2135

  摘要：

  DOI：

文献信息

• REYMOND, JEAN-LOUIS;VOGEL, PIERRE, TETRAHEDRON LETT., 30,(1989) N, C. 705-706
  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：——
• 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.