(1S)-2-exo,3-endo-diacetoxy-5-endo-acetoxymethyl-7-oxabicyclo<2.2.1.>heptane | 90695-20-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (1S)-2-exo,3-endo-diacetoxy-5-endo-acetoxymethyl-7-oxabicyclo<2.2.1.>heptane
• 英文别名: (1S)-2-exo,3-endo-diacetoxy-5-endo-acetoxymethyl-7-oxabicyclo[2.2.1]heptane；(1S)-2-exo,3-endo-diacetoxy-5-endo-acetoxymethyl-7-oxabicyclo[2.2.1.]heptane；exo-2, endo-3-diacetoxy-endo-5-acetoxymethyl-7-oxabicyclo[2.2.1]heptane
• CAS: 90695-20-8；64589-25-9；117772-63-1；117772-66-4
• 化学式: C₁₃H₁₈O₇
• 分子量: 286.282
• InChiKey: URJPMEBENDGKSF-FHUSYTEZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  20.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  88.13
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  (1S)-2-exo,3-endo-diacetoxy-5-endo-acetoxymethyl-7-oxabicyclo<2.2.1.>heptane 在 吡啶 、 硫酸 、 sodium methylate 、 对甲苯磺酸 、 溶剂黄146 、 N,N-二异丙基乙胺 作用下， 以 甲醇 、 二氯甲烷 、 溶剂黄146 、 N,N-二甲基甲酰胺 为溶剂， 反应 108.5h， 生成 1-O-acetyl-2,3,4,6-tetra-O-methoxymethyl-5a-carba-β-D-galactopyranose
  参考文献：
  名称：

  Synthesis of an ether-linked alkyl 5a-carba-β-d-glucoside, a 5a-carba-β-d-galactoside, a 2-acetamido-2-deoxy-5a-carba-β-d-glucoside, and an alkyl 5a′-carba-β-lactoside

  摘要：

  For the purpose of providing biologically stable building blocks for the biocombinatorial synthesis using a living cell, some ether-linked alkyl 5a-carba-beta-D-glycoside primers were prepared. The key step of the synthesis was coupling of 1-bromo-n-alkanes with the 1-OH unprotected derivatives of 5a-carba-sugar analogues of D-glucose, D-galactose, and 2-acetamido-2-deoxy-D-glucose (N-acetyl-D-glucosamine). in DMF in the presence of sodium hydride. Alternatively, alkyl carba-lactoside was synthesized by incorporation of a 5a-carba-beta-D-galactose residue into the 4-position of dodecyl beta-D-glueopyranoside, A strong and specific inhibition of beta-galactosidase (K-i 0.67 muM bovine liver) was found for dodecyl 5a-carba-beta-D-galactopyranoside. (C) 2002 Elsevier Science Ltd. All rights reserved,

  DOI：

  10.1016/s0008-6215(02)00294-x
• 作为产物：
  描述：

  2,2-dimethylpropanoyloxymethyl (1R,2R,4R)-7-oxabicyclo[2.2.1]hept-5-ene-2-carboxylate 在 吡啶 、 4-二甲氨基吡啶 、 sodium hydroxide 、 lithium aluminium tetrahydride 、 甲酸 、 phosphate buffer 、 pig liver esterase 、 水 、 双氧水 作用下， 以 四氢呋喃 、 叔丁醇 为溶剂， 反应 22.0h， 生成 (1S)-2-exo,3-endo-diacetoxy-5-endo-acetoxymethyl-7-oxabicyclo<2.2.1.>heptane
  参考文献：
  名称：

  Hydrolytic enzymes in the synthesis of carba-sugars: application of the lipase from Pseudomonas fragi

  摘要：

  猪肝酯酶催化的(±)-内-2-甲氧基羰基-7-氧杂双环[2.2.1]庚-5-烯 1a 的水解产物为(-)-内-7-氧杂双环[2.2.1]庚-5-烯-2-羧酸 1b 和(+)-内-2-甲氧基羰基-7-氧杂双环[2.2.1]庚-5-烯 1a，ee 分别为 36% 和 57%。在假单胞菌 fragi 的脂肪酶催化下，(±)-2-外-羟基-4,8-二氧三环[4.2.1.03,7]壬-5-酮 2a 与乙酸乙烯酯发生酯交换反应，生成的乙酸酯 (-)-2b 和醇 (+)-2a 的ee值分别为 91% 和 94%。(-)-2b(ee)为 91%（EtOH），从不纯物醋酸酯中除去污染性外消旋物后结晶，得到光学纯度很高的醋酸酯 (-)-2b。

  DOI：

  10.1039/a708593a

文献信息

• Total synthesis of (+)-(1,2,3/4,5)-2,3,4,5-tetrahydroxycyclohexane-1-methanol and (+)-(1,3/2,4,5)-5-amino-2,3,4-trihydroxycyclohexane-1-methanol [(+)-validamine]. X-Ray crystal structure of (3S)-(+)-2-exo-bromo-4,8-dioxatricyclo[4.2.1.O]nonan-5-one
  作者：Seiichiro Ogawa、Yoshikazu Iwasawa、Taisuke Nose、Tetsuo Suami、Shigeru Ohba、Masatoki Ito、Yoshihiko Saito

  DOI：10.1039/p19850000903

  日期：——

  1]hept-5-ene-2-carboxylic acid (±)-(1) has been accomplished by use of (R)-(+)- and (S)-(–)-α-methylbenzylamine, respectively. The absolute configuration of (–)-(1) has been determined on the basis of X-ray analysis of the bromo lactone (2) derived from it. The title branched-chain cyclitol (6), the antibiotic produced by Streptomyces sp. MA-4145, has been totally synthesized from (–)-(1), its absolute configuration

  （±）-7-内-氧杂双环[2.2.1]庚-5-烯-2-羧酸（±）-（1）的光学拆分已通过使用（R）-（+）-和（S）-（-）-α-甲基苄胺。（-）-（1）的绝对构型是根据对其衍生的溴内酯（2）的X射线分析确定的。标题支链环醇（6），由链霉菌属产生的抗生素。MA-4145已完全由（–）-（1）合成，其绝对构型已确定。所述五的合成Ñ，ö还通过（-）-（1）进行了（+）-有效胺的-乙酰基衍生物（12），该胺是通过抗生素有效霉素A降解获得的支链氨基环糖醇。
• TOTAL SYNTHESIS AND ABSOLUTE CONFIGURATION OF (+)-(1,2,3/4,5)-2,3,4,5-TETRAHYDROXY-1-CYCLOHEXANEMETHANOL
  作者：Seiichiro Ogawa、Yoshikazu Iwasawa、Tetsuo Suami

  DOI：10.1246/cl.1984.355

  日期：1984.3.5

  The title branched-chain cyclitol has been synthesized from chiral 7 endo-oxabicyclo[2.2.1]hept-5-ene-2-carboxylic acid, the absolute configuration of which was established on the basis of X-ray analysis of crystalline bromolactone derived from it. From this result the C-1 configuration of the cyclitol is determined to be R.

  标题的支链环醇是通过手性7-内-氧双环[2.2.1]庚-5-烯-2-羧酸合成的，其绝对构型是基于从中衍生的晶体溴内酯的X射线分析来确定的。由此结果可确定环醇的C-1构型为R。
• Pseudo-sugars. VI. Synthesis of Six Isomers of 5-Hydroxymethyl-1,2,3,4-cyclohexanetetrol (Pseudo-hexopyranose) and Their Derivatives
  作者：Seiichiro Ogawa、Masayasu Ara、Takashi Kondoh、Michio Saitoh、Reiko Masuda、Tatsushi Toyokuni、Tetsuo Suami

  DOI：10.1246/bcsj.53.1121

  日期：1980.4

  Six isomers of 5-hydroxymethyl-1,2,3,4-cyclohexanetetrol, including naturally occurring (1,2/3,4,5)-isomer, and their several derivatives were synthesized from the exo-2-substituted endo-3-acetoxy-endo-5-acetoxymethyl-7-oxabicyclo[2.2.1]heptane compounds.

  从外向-2-取代内向-3-乙酰氧基-内向-5-乙酰氧甲基-7-氧杂双环[2.2.1]庚烷化合物中合成了六种 5-羟甲基-1,2,3,4-环己烷四醇异构体（包括天然存在的 (1,2/3,4,5) -异构体）及其多种衍生物。
• Pseudo-sugars. 4. A Facile Synthesis of DL-Validamine and Its Derivative
  作者：Seiichiro Ogawa、Koji Nakamoto、Masaaki Takahara、Yoshio Tanno、Noritaka Chida、Tetsuo Suami

  DOI：10.1246/bcsj.52.1174

  日期：1979.4

  Penta-N,O-acetyl-Dl-validamine was prepared from readily available endo-2, exo-3-diacetoxy-endo-6-acetoxymethyl-7-oxabicyclo[2.2.1]heptane in three steps in an overall yield of 36%.

  五-N,O-乙酰基-D1-有效胺由容易获得的内-2,外-3-二乙酰氧基-内-6-乙酰氧基甲基-7-氧杂二环[2.2.1]庚烷分三步制备，总产率为36 %。