6-Deoxycastanospermine | 130948-07-1

• 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-Deoxycastanospermine
• 英文别名: (1S,7R,8R,8aR)-1,2,3,5,6,7,8,8a-octahydroindolizine-1,7,8-triol
• CAS: 130948-07-1
• 化学式: C₈H₁₅NO₃
• 分子量: 173.212
• InChiKey: UOCBJSROECMAOQ-OSMVPFSASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.3
• 重原子数：
  12
• 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：
  4

反应信息

• 作为产物：
  描述：

  (1S,6S,7S,8R,8aS)-8-(Benzyloxy)-6,7-epoxy-1-hydroxyoctahydroindolizidin-5-one 在 palladium on activated charcoal 盐酸 、 dimethyl sulfide borane 、 氢气 作用下， 以 甲醇 、 甲酸 、 水 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 20.0h， 生成 6-Deoxycastanospermine
  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

• 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 synthesis of (±)-6-deoxycastanospermine: an application of the addition of organoboronates to N-acyliminium ions
  作者：Robert A Batey、D.Bruce MacKay

  DOI：10.1016/s0040-4039(00)01790-1

  日期：2000.12

  An efficient synthesis of (±)-6-deoxycastanospermine is reported, using a diastereoselective coupling of organoboronates with N-acyliminium ions as the key step. The construction of the indolizidine ring system is completed using a subsequent reductive amination reaction.

  据报道，使用有机硼酸酯与N-酰基亚胺离子的非对映选择性偶联作为关键步骤，可以有效合成（±）-6-脱氧卡那曲胺。使用随后的还原性胺化反应完成吲哚并咪唑环系统的构建。
• A chemoenzymatic synthesis of (+)-castanospermine
  作者：Rojeev Bhide、Reza Mortezaei、A. Scilimati、Charles J. Sih

  DOI：10.1016/s0040-4039(00)97743-8

  日期：1990.1
• 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：——
• BHIDE, ROJEEV;MORTEZAEI, REZA;SCILIMATI, A.;SIH, CHARLES J., TETRAHEDRON LETT., 31,(1990) N4, C. 4827-4830
  作者：BHIDE, ROJEEV、MORTEZAEI, REZA、SCILIMATI, A.、SIH, CHARLES J.

  DOI：——

  日期：——