(1S,4S,5S,6S)-6-Benzyloxy-5-bromo-7-oxa-bicyclo[2.2.1]heptan-2-one

• 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: (1S,4S,5S,6S)-6-Benzyloxy-5-bromo-7-oxa-bicyclo[2.2.1]heptan-2-one
• 英文别名: (1S,4S,5S,6S)-5-bromo-6-phenylmethoxy-7-oxabicyclo[2.2.1]heptan-2-one
• 化学式: C₁₃H₁₃BrO₃
• 分子量: 297.148
• InChiKey: VVRNNVUGCJGLNI-WUHRBBMRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1S,4S,5S,6S)-6-Benzyloxy-5-bromo-7-oxa-bicyclo[2.2.1]heptan-2-one 在 三乙胺 作用下， 以 乙腈 为溶剂， 反应 0.5h， 以60%的产率得到(+/-)-(1RS,4SR,6SR)-6-endo-benzyloxy-7-oxabicyclo[2.2.1]heptan-2-one
  参考文献：
  名称：

  在三乙胺的存在下，通过烷基卤的照射形成自由基。在合成（±）-双硼苯醌中的应用

  摘要：

  在三乙胺的存在下照射不饱和卤化物导致形成相应的环化产物。该光还原环化已用于合成（±）-双硼苯醌的双环核。

  DOI：

  10.1016/s0040-4020(01)00357-x
• 作为产物：
  描述：

  7-oxabicyclo<2.2.1>hept-5-en-2-one dibenzyl acetal 在 溴 、 碳酸氢钠 作用下， 生成 (1S,4S,5S,6S)-6-Benzyloxy-5-bromo-7-oxa-bicyclo[2.2.1]heptan-2-one
  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

文献信息

• A highly stereoselective total synthesis of (±)castanospermine
  作者：Jean-Louis Reymond、Pierre Vogel

  DOI：10.1016/s0040-4039(01)80287-2

  日期：——

  An efficient synthesis of (±)castanospermine based on the bromine addition to 7-oxabicyclo[2.2.1]hept-5-en-2-one benzyl acetal is presented.

  提出了一种有效的合成方法，基于将溴加成7-氧杂双环[2.2.1]庚-5-烯-2-酮苄基缩醛，合成（±）castanospermine。
• 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）。
• REYMOND, JEAN-LOUIS;VOGEL, PIERRE, TETRAHEDRON LETT., 30,(1989) N, C. 705-706
  作者：REYMOND, JEAN-LOUIS、VOGEL, PIERRE

  DOI：——

  日期：——
• Formation of radicals by irradiation of alkyl halides in the presence of triethylamine. Application to the synthesis of (±)-bisabolangelone
  作者：Janine Cossy、Véronique Bellosta、Jean-Luc Ranaivosata、Barbara Gille

  DOI：10.1016/s0040-4020(01)00357-x

  日期：2001.6

  The irradiation of unsaturated halides in the presence of triethylamine leads to the formation of the corresponding cyclized products. This photoreductive cyclization has been used to synthesize the bicyclic core of (±)-bisabolangelone.

  在三乙胺的存在下照射不饱和卤化物导致形成相应的环化产物。该光还原环化已用于合成（±）-双硼苯醌的双环核。
• 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.