(+/-)-methyl 3,4-O-isopropylidene-6-epishikimate | 88165-26-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-methyl 3,4-O-isopropylidene-6-epishikimate
• 英文别名: (+/-)-3,4-O,O-isopropylidine-1-methoxycarbonyl-3α,4α,5α-trihydroxycyclohexene；methyl (3aR,7S,7aS)-7-hydroxy-2,2-dimethyl-3a,6,7,7a-tetrahydro-1,3-benzodioxole-5-carboxylate
• CAS: 88165-26-8；88587-13-7；92936-06-6；99862-07-4；109430-30-0；141393-61-5；141781-67-1
• 化学式: C₁₁H₁₆O₅
• 分子量: 228.245
• InChiKey: BPQMQIJLKGETOF-YIZRAAEISA-N

物化性质

• 沸点：
  343.2±42.0 °C(Predicted)
• 密度：
  1.220±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (+/-)-methyl 3,4-O-isopropylidene-6-epishikimate 在 alkaline hydrogen peroxide 、 三苯基膦 、 diborane(6) 、 偶氮二甲酸二乙酯 作用下， 生成 (+/-)-methyl shikimate
  参考文献：
  名称：

  Complementary short syntheses of (±)-methyl shikimate

  摘要：

  DOI：

  10.1016/s0040-4039(01)90029-2
• 作为产物：
  描述：

  Methyl (1R,2R,3S,4S,5R)-2,3-O,O-isopropylidene-2,3-dihydroxy-7-oxabicyclo<2.2.1>heptane-5-carboxylate 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 (+/-)-methyl 3,4-O-isopropylidene-6-epishikimate
  参考文献：
  名称：

  Rajapaksa, D.; Keay, B. A.; Rodrigo, R., Canadian Journal of Chemistry, 1984, vol. 62, p. 826 - 828

  摘要：

  DOI：

文献信息

• Enantiospecific synthesis of (-)-5-epi-shikimic acid and a new route to (-)-shikimic acid
  作者：Shende Jiang、Boualem Mekki、Gurdial Singh、Richard H. Wightman

  DOI：10.1016/s0040-4039(00)73536-2

  日期：1994.7

  (-)-Shikimic acid (1) and (-)-5-epi-shikimic acid (2) have each been prepared enantiospecifically and with high diastereoselectivity from D-ribose.

  （-）-Shikimic acid（1）和（-）-5- epi- shikimic acid（2）分别从D-核糖中对映体特异性和高非对映选择性地制备。
• Enantiospecific synthesis of (−)-5-epi-shikimic acid and (−)-shikimic acid
  作者：Shende Jiang、Kevin J. McCullough、Boualem Mekki、Gurdial Singh、Richard H. Wightman

  DOI：10.1039/a700389g

  日期：——

  Diastereoselective reaction of 2,3-O-isopropylidene-D-ribose with allylmagnesium chloride gave a 5∶1 mixture of triols 4 and 5, which were then converted to nitrones 8 and 9. Intramolecular nitrone cycloaddition gave the isoxazolidines 10 and 11, which on acetylation gave the corresponding acetates 12 and 13 which were separated by repeated crystallisation. The major adduct 12 was converted to (-)-5-epi-shikimic acid 2. Reaction of the ribonolactone derivative 20 with allylmagnesium chloride gave the hemiacetal 21. Reduction of compound 21 with DIBAL afforded exclusively the diol 22, which was desilylated to give the triol 5. Similar chemistry to that employed for the synthesis of (-)-5-epi-shikimic acid 2 with the diol 5 resulted in the synthesis of (-)-shikimic acid 1.

  2,3-O-异亚丙基-D-核糖与烯丙基氯化镁发生非对映选择性反应，生成 5∶1 的三醇混合物 4 和 5，然后转化为硝酮 8 和 9。分子内的硝酮环化反应生成异噁唑烷 10 和 11，乙酰化反应生成相应的乙酸盐 12 和 13，通过反复结晶分离。主要加合物 12 转化为 (-)-5- 表莽草酸 2。核糖酸内酯衍生物 20 与烯丙基氯化镁反应生成半缩醛 21。 化合物 21 与二乙酰胆碱还原生成二元醇 22，二元醇 22 经过脱硅反应生成三元醇 5。用二元醇 5 合成(-)-5-表莽草酸 2 的化学反应与合成(-)-莽草酸 1 的化学反应类似。
• Reactivity studies in the shikimic acid series: The synthesis of racemic methyl 6α-fluoroshikimate
  作者：Stephen A. Bowles、Malcolm M. Campbell、Malcolm Sainsbury、Gareth M. Davies

  DOI：10.1016/s0040-4020(01)90533-2

  日期：1990.1

  The regio- and stereo-selective epoxidation of methyl 3,4-dihydrobenzoate derivatives has been investigated. Perbenzimidic acid leads only to epoxides formed at the Δ1,2 bond. More electrophilic reagents such as MCPBA also give products of this type, as well as epoxides formed through attack at the Δ5,6 bond. Reactions of the 3,4-dihydrobenzoates with thiophenate anion have been undertaken as a means

  已经研究了3，4-二氢苯甲酸甲酯衍生物的区域和立体选择性环氧化。Perbenzimidic酸仅导致在Δ形成环氧化物1,2-键。更多的亲电试剂（例如MCPBA）也可以提供这种类型的产物，以及通过攻击Δ5,6键形成的环氧化物。3,4- dihydrobenzoates与thiophenate阴离子的反应已经进行作为保护Δ的手段1,2-键，并由此控制环氧化的区域选择性。通过3，4-二氢-3，4-异丙基二烯二氧基苯甲酸甲酯的环氧化物的开环，已经实现了外消旋6α-氟代草酸甲酯的合成。
• Examination of the Reactivity of Hydroxy Groups in Multioxygenated Cyclohexanoids: Synthetic Study toward Cytotoxic Pericosine B
  作者：Yoshihide Usami、Atsushi Numata

  DOI：10.1248/cpb.52.1125

  日期：——

  The reactivity of two hydroxy groups in some multioxygenated cyclohexanoids was examined for basic study of the synthesis of the cytotoxic marine natural product pericosine B and related compounds. Differences in reactivity for O-methylation or O-acylation among substrates were observed.

  为了对具有细胞毒性的海洋天然产物包心苷 B 和相关化合物的合成进行基础研究，对一些多氧环己烷中两个羟基的反应性进行了研究。观察到不同底物的 O-甲基化或 O-酰化反应性存在差异。
• Brief syntheses of (±)-methyl shikimate, (±)-methyl epishikimate and structural variants
  作者：Malcolm M. Campbell、Aston D. Kaye、Malcolm Sainsbury、Roya Yavarzadeh

  DOI：10.1016/s0040-4020(01)83498-0

  日期：1984.1