(1R)-(+)-(1,2,3/4,5)-2,3,4,5-tetrahydroxycyclohexane-1-methanol penta-acetate | 52079-86-4

• 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: (1R)-(+)-(1,2,3/4,5)-2,3,4,5-tetrahydroxycyclohexane-1-methanol penta-acetate
• 英文别名: 1,2,3,4,6-penta-O-acetyl-5a-carba-α-D-galactopyranose；5a-carba-α-D-galactose pentaacetate；Pseudo-α-D-galactopyranose-pentaacetat；[(1R,2S,3S,4S,5S)-2,3,4,5-tetraacetyloxycyclohexyl]methyl acetate
• CAS: 52079-86-4
• 化学式: C₁₇H₂₄O₁₀
• 分子量: 388.372
• InChiKey: NHQQATCRVHXHKV-XAJHFOFHSA-N

物化性质

• 沸点：
  420.2±38.0 °C(predicted)
• 密度：
  1.26±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  27
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  132
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  (1R)-(+)-(1,2,3/4,5)-2,3,4,5-tetrahydroxycyclohexane-1-methanol penta-acetate 在 吡啶 、 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 、 N,N-二甲基甲酰胺 为溶剂， 反应 89.5h， 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：

  1L-3-Desoxy-1,2:5,6-di-O-isipropyliden-3-C-<(2-methoxyethoxy)methoxymethyl>-allo-inosit-4-(S-methyldithiocarbonat) 在 盐酸 、 三正丁基氢锡 作用下， 以 甲苯 为溶剂， 反应 40.0h， 生成 (1R)-(+)-(1,2,3/4,5)-2,3,4,5-tetrahydroxycyclohexane-1-methanol penta-acetate
  参考文献：
  名称：

  Paulsen, Hans; Deyn, Wolfgang von; Roeben, Wolfgang, Liebigs Annalen der Chemie, 1984, # 3, p. 433 - 449

  摘要：

  DOI：

文献信息

• A Stereodivergent Approach to 5a-Carba-α-D-gluco-, -α-D-galacto and -β-L-gulopyranose Pentaacetates fromD-Mannose, Based on 6-exo-dig Radical Cyclization and Barton−McCombie Radical Deoxygenation
  作者：Ana M. Gómez、Eduardo Moreno、Serafín Valverde、J. Cristóbal López

  DOI：10.1002/ejoc.200300339

  日期：2004.4

  The three carbasugars, 5a-carba-α-D-gluco-, -α-D-galacto and -β-L-gulopyranose pentaacetates 42, 35 and 28 respectively, have been prepared in a stereodivergent manner from D-mannose. Alkynyl derivatives of 2,3:4,6-di-O-isopropylidene-D-mannopyranose, which are homologated at C-1 by reaction with trimethylsilylacetylide, undergo a 6-exo-dig radical cyclization, from a radical located at C-5, to yield

  三种碳水化合物，5a-carba-α-D-葡萄糖-、-α-D-半乳糖和-β-L-吡喃葡萄糖五乙酸酯分别为 42、35 和 28，已从 D-甘露糖以立体发散方式制备。2,3:4,6-二-O-异亚丙基-D-吡喃甘露糖的炔基衍生物，通过与三甲基甲硅烷基乙炔反应在C-1处同系化，从位于C-的自由基经历6-exo-dig自由基环化5，得到高度官能化的外-亚甲基环己烷的混合物。后者中环外双键的臭氧分解产生环己酮，通过羰基部分的立体选择性还原，然后在 C-4 或 C-5a 位（母体碳水化合物编号）进行位点选择性脱氧，得到标题碳糖。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• A general stereodivergent strategy for the preparation of carbasugars. Syntheses of 5a-carba-α-d-glucose, α-d-galactose, and β-l-gulose pentaacetates from d-mannose
  作者：Ana M. Gómez、Eduardo Moreno、Serafı́n Valverde、J.Cristóbal López

  DOI：10.1016/s0040-4039(02)01121-8

  日期：2002.8

  A stereodivergent approach to 5a-carba-d- and l-pyranoses has been applied to the preparation of 5a-carba-α-d-gluco-, 5a-carba-α-d-galacto-, and 5a-carba-β-l-gulopyranose pentaacetates. The strategy, by which a single precursor can be transformed into three different carbasugars, features a stereoselective reduction followed by deoxygenation of a key polyoxygenated methylcyclohexanone intermediate

  5a-氨基甲酸酯-d-和1-吡喃糖的立体发散方法已用于制备5a-氨基甲酸酯-α-d-葡萄糖，5a-氨基甲酸酯-α-d-半乳糖和5a-氨基甲酸酯-β-左旋吡喃葡萄糖五乙酸盐。该策略可将单个前体转化为三个不同的Carbasugars，其特征是立体选择性还原，然后对关键的多氧化甲基环己酮中间体进行脱氧。后者可容易地通过d-甘露糖衍生物的6- ex - dig自由基环化获得。
• 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。
• Synthesis of some derivatives of pseudo-α-galactopyranose [(1,2/3,4,5)-5-hydroxymethyl-1,2,3,4-cyclohexanetetrol]
  作者：Seiichiro Ogawa、Yasushi Shibata、Keiko Miyazawa、Tatsuhi Toyokuni、Tatsuo Iida、Tetsuo Suami

  DOI：10.1016/0008-6215(87)80164-7

  日期：1987.6

  -isopropylidene derivatives. Several C-7 substituted derivatives of 1 of biological interest have been prepared by nucleophilic displacement reactions of the tosylate derived from the most readily available 1,2:3,4-di- O -isopropylidene derivative 3 . Condensation of 3 with 2,3,4,6-tetra- O -acetyl-α- d -glucopyranosyl bromide gave diastereoisomeric products, which were converted into 7- O -(β- d -glucopyranosyl)-pseudo-α-

  摘要在甲苯存在下，N，N-二甲基甲酰胺中的2,2-二甲氧基丙烷与dl-（1,2 / 3,4,5）-5-羟甲基-1,2,3,4-环己烷四醇（1）进行异丙基化-对磺酸得到1,2：3,4-，1,2：4,7-和2,3：4,7-二-O-异亚丙基衍生物。通过从最容易获得的1,2：3,4-二-O-异亚丙基衍生物3衍生的甲苯磺酸酯的亲核取代反应，已经制备了一些具有生物学意义的1的C-7取代衍生物。3与2,3,4,6-四-O-乙酰基-α-d-吡喃葡萄糖基溴的缩合得到非对映异构产物，将其转化为7-O-（β-d-吡喃葡萄糖基）-伪α-d- （26a）和-d-吡喃半乳糖（26B），其结构通过26A的八乙酸酯的降解得到证实，产生已知的伪α-d-吡喃半乳糖五乙酸酯。