(+)-Methyl 3,4-O-cyclohexylidene-5-didehydroshikimate | 168961-20-4

• 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 (3aS,7aS)-7-oxospiro[6,7a-dihydro-3aH-1,3-benzodioxole-2,1'-cyclohexane]-5-carboxylate
• CAS: 168961-20-4
• 化学式: C₁₄H₁₈O₅
• 分子量: 266.294
• InChiKey: MABXLCJUBYYCFC-NWDGAFQWSA-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 作用下， 以 甲醇 为溶剂， 生成 Methyl (3S,4R,5R)-3,4-O-cyclohexylidene-3,4-epi-shikimate
  参考文献：
  名称：

  Aiming for Branimycin: Synthesis of thecis-Decalin Core

  摘要：

  以奎宁酸为起点，合成了一种高度取代的顺式δ,δ² 不饱和氧化腈，并通过 1,3-二极环加成反应得到了布兰霉素的顺式癸醛系统前体。

  DOI：

  10.1055/s-2005-872222
• 作为产物：
  描述：

  Methyl 4,5-O-cyclohexylidene-3-didehydro-4-epi-shikimate 在 sodium tetrahydroborate 、 戴斯-马丁氧化剂 、 对甲苯磺酸 作用下， 以 甲醇 为溶剂， 生成 (+)-Methyl 3,4-O-cyclohexylidene-5-didehydroshikimate
  参考文献：
  名称：

  Studies toward the construction of the allyltrisulfide Component in esperamicin-A1 from 5-ketoshikimic acid derivatives: Part 1

  摘要：

  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.

  DOI：

  10.1016/s0040-4039(98)02399-5

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.