(-)-Methyl 3,4-O-cyclohexylidene-5-didehydroshikimate | 168784-03-0

• 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-cyclohexylidene-5-didehydroshikimate
• 英文别名: methyl (3aR,7aR)-7-oxospiro[6,7a-dihydro-3aH-1,3-benzodioxole-2,1'-cyclohexane]-5-carboxylate
• CAS: 168784-03-0
• 化学式: C₁₄H₁₈O₅
• 分子量: 266.294
• InChiKey: MABXLCJUBYYCFC-NEPJUHHUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (-)-Methyl 3,4-O-cyclohexylidene-5-didehydroshikimate 在 sodium tetrahydroborate 、 三氟乙酸 作用下， 以 甲醇 、 水 为溶剂， 反应 1.0h， 生成 (+/-)-methyl 5-epishikimate
  参考文献：
  名称：

  从（-）-奎宁酸合成新的高效对映体特异性的（-）-5- epi- shikimate甲基和5- epi- quinate甲基

  摘要：

  （ - ） - 5-外延-shikimate和5-外延-quinate从容易得到的和便宜的有效地合成（ - ） -奎尼酸1作为反应的新的，短而简单的序列的常见原料。

  DOI：

  10.1016/s0040-4039(97)01109-x
• 作为产物：
  描述：

  methyl (3aS,4R,7aR)-4-hydroxy-3a,4,5,7a-tetrahydrospiro[benzo[d][1,3]dioxole-2,1'-cyclohexane]-6-carboxylate 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 (-)-Methyl 3,4-O-cyclohexylidene-5-didehydroshikimate
  参考文献：
  名称：

  从（-）-奎宁酸合成新的高效对映体特异性的（-）-5- epi- shikimate甲基和5- epi- quinate甲基

  摘要：

  （ - ） - 5-外延-shikimate和5-外延-quinate从容易得到的和便宜的有效地合成（ - ） -奎尼酸1作为反应的新的，短而简单的序列的常见原料。

  DOI：

  10.1016/s0040-4039(97)01109-x

文献信息

• Construction of the Bicyclic Core Structure of the Enediyne Antibiotic Esperamicin-A1 in Either Enantiomeric Form from (-)-Quinic Acid
  作者：Gerardo Ulibarri、William Nadler、Troels Skrydstrup、Helene Audrain、Angele Chiaroni、Claude Riche、David S. Grierson

  DOI：10.1021/jo00114a025

  日期：1995.5

  Employed as a common chiral starting material, (-)-quinic acid (7) was converted in a concise manner to both enantiomers of the beta,gamma-unsaturated ketone 12. On the one hand, (+)-12 was obtained by stereospecific borohydride reduction of the conjugated ketone intermediate 9, transketalization, and oxidation of the derived homoallylic alcohol using the Dess-Martin periodinane reagent. Alternatively, dehydration of the tertiary alcohol 13 and oxidation of the free hydroxyl group in 14 furnished (-)-12 in good overall yield. Reaction of (+)-12 with dichlorocerium TMS acetylide was followed by Pd(0)-assisted construction of the acyclic enediyne 21. Cyclization of this intermediate on treatment with KHMDS proved efficient, providing the esperamicin intermediate (-)-22 in 60% isolated yield. In an identical fashion -)-12 was converted to the enantiomeric bicyclic enediyne (+)-22. Subsequent liberation of the diol system, and selective oxidation of the allylic alcohol in 25 gave ketone 26. Reaction of this intermediate with Ph(2)S=NH monohydrate gave aziridine 27 which was readily converted to its carbamate derivative 28 in preparation for aziridine ring opening.
• Studies toward the construction of the allyltrisulfide Component in esperamicin-A1 from 5-ketoshikimic acid derivatives: Part 1
  作者：Sandrine Piguel、Gerardo Ulibarri、David S. Grierson

  DOI：10.1016/s0040-4039(98)02399-5

  日期：1999.1

  The conversion of keto ester 1, obtained in either enantiomeric form from (-)-quinic acid to its corresponding enol silyl ether 4 was examined as the first step to construct the allyl trisulfide unit found in esperamicin A,. Under different conditions a very facile dimerization of either 4 or enolate 10 to give compound 14 was observed. (C) 1998 Elsevier Science Ltd. All rights reserved.
• First Total Synthesis of Antitumor Natural Product (+)- and (−)-Pericosine A:  Determination of Absolute Stereo Structure^†
  作者：Yoshihide Usami、Isao Takaoka、Hayato Ichikawa、Yusuke Horibe、Syunsuke Tomiyama、Misako Ohtsuka、Yumi Imanishi、Masao Arimoto

  DOI：10.1021/jo070715l

  日期：2007.8.1

  The first total synthesis of (+)- and (−)-pericosine A has been achieved, enabling the revision and determination of the absolute configuration of this antitumor natural product as methyl (3S,4S,5S,6S)-6-chloro-3,4,5-trihydroxy-1-cyclohexene-1-carboxylate. Every step of this total synthesis proceeded well with excellent stereoselectivity. Structures of the intermediates in crucial steps were confirmed

  已完成（+）-和（-）-pericosine A的第一个全合成，从而能够修订和确定该抗肿瘤天然产物的绝对构型，即甲基（3 S，4 S，5 S，6 S）- 6-氯-3,4,5-三羟基-1-环己烯-1-羧酸酯。该全合成的每一步都以优异的立体选择性进行得很好。关键步骤中的中间体结构通过详细的2D NMR分析得到确认。
• New and efficient enantiospecific synthesis of (−)-Methyl 5-epi-shikimate and methyl 5-epi-quinate from (−)-quinic acid
  作者：Susana Fernández、Mónica Díaz、Miguel Ferrero、Vicente Gotor

  DOI：10.1016/s0040-4039(97)01109-x

  日期：1997.7

  (−)-Methyl 5-epi-shikimate and methyl 5-epi-quinate were synthesized efficiently from readily available and inexpensive (−)-quinic acid 1 as a common starting material on a new, short and simple sequence of reactions.

  （ - ） - 5-外延-shikimate和5-外延-quinate从容易得到的和便宜的有效地合成（ - ） -奎尼酸1作为反应的新的，短而简单的序列的常见原料。