methyl (3aS,4R,7aR)-4-hydroxy-3a,4,5,7a-tetrahydrospiro[benzo[d][1,3]dioxole-2,1'-cyclohexane]-6-carboxylate | 120200-03-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (3aS,4R,7aR)-4-hydroxy-3a,4,5,7a-tetrahydrospiro[benzo[d][1,3]dioxole-2,1'-cyclohexane]-6-carboxylate
• 英文别名: methyl (3R,4S,5R)-3,4-O-cyclohexylidene-3,4,5-trihydroxy-1-cyclohexene-1-carboxylate；Methyl 3,4-O-cyclohexylideneshikimate；methyl (3aR,7R,7aS)-7-hydroxyspiro[3a,6,7,7a-tetrahydro-1,3-benzodioxole-2,1'-cyclohexane]-5-carboxylate
• CAS: 120200-03-5
• 化学式: C₁₄H₂₀O₅
• 分子量: 268.31
• InChiKey: WXHNAVBCFPZHBX-UTUOFQBUSA-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：
  0.79
• 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 (3aS,4R,7aR)-4-hydroxy-3a,4,5,7a-tetrahydrospiro[benzo[d][1,3]dioxole-2,1'-cyclohexane]-6-carboxylate 在 sodium tetrahydroborate 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 3.0h， 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：

  右旋奎宁酸 在 吡啶 、 氯化亚砜 、 硫酸 、 对甲苯磺酸 作用下， 以 1,4-二氧六环 、 甲醇 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 methyl (3aS,4R,7aR)-4-hydroxy-3a,4,5,7a-tetrahydrospiro[benzo[d][1,3]dioxole-2,1'-cyclohexane]-6-carboxylate
  参考文献：
  名称：

  An Efficient Transformation of (-)-Quinic Acid into Carba-l-rhamnose

  摘要：

  描述了一种从 (-)-奎尼酸立体选择性合成卡巴-l-鼠李糖的新方法。获得具有适当模式的保护基团的标题化合物，用于制备肺炎链球菌19F型荚膜多糖重复单元。

  DOI：

  10.1055/s-2004-834825

文献信息

• 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。
• Synthesis of Marine Natural Product (−)-Pericosine E
  作者：Koji Mizuki、Kaoru Iwahashi、Naoko Murata、Mayuko Ikeda、Yutaka Nakai、Hiroki Yoneyama、Shinya Harusawa、Yoshihide Usami

  DOI：10.1021/ol501631r

  日期：2014.7.18

  The first synthesis of (−)-pericosine E (6), a metabolite of the Periconia byssoides OUPS-N133 isolated originally from the sea hare Aplysia kurodai, has been achieved. Efficient and regioselective synthetic procedures for the synthesis of key intermediates, anti- and syn-epoxides 9 and 10, were developed using an anti-epoxidation of diene 12 with TFDO and a bromohydrination of 12 with NBS in CH3CN/H2O

  已实现（-）-pericosine E（6）的首次合成，E-pericosine E（6）是最初从海兔Aplysia kurodai分离得到的Periconia byssoides OUPS-N133的代谢物。为关键中间体的合成，有效和区域选择性的合成方法的抗与顺式环氧化物9和10，分别使用开发抗二烯-epoxidation 12与TFDO和的bromohydrination 12与NBS在CH 3 CN / H 2 O（ 2：3）。此外，合成6的特定旋光度比较天然6阐明，天然优选的Percosine E对映异构体具有与由氯代醇（-）- 8和抗环氧（+）- 9合成的（-）- 6相同的绝对构型。
• An Electrophilic Natural Product Provides a Safe and Robust Odor Neutralization Approach To Counteract Malodorous Organosulfur Metabolites Encountered in Skunk Spray
  作者：Lin Du、Charissa Munteanu、Jarrod B. King、Doug E. Frantz、Robert H. Cichewicz

  DOI：10.1021/acs.jnatprod.9b00415

  日期：2019.7.26

  The anal secretions of skunks comprise several types of malodorous organosulfur compounds. The pungent metabolites are used defensively by skunks to repel threats posed by predators, and in many parts of the world, those perceived threats include humans and their pets. The extremely low thresholds for detection of the organosulfur metabolites make efforts to "de-skunk" people, animals, and clothing a process fraught with many challenges. The fungal-derived metabolite pericosine A (4) is a promiscuous yet stabile electrophilic compound that we propose is used by some fungi as a novel form of chemical defense. Our investigations have indicated that pericosine A readily reacts with skunk-spray secretions to transform them into odorless products. Mechanistic and computational studies suggested that pericosine A and its synthetic analogues react via S_N2'-type mechanisms with thiols and thioacetates under aqueous conditions to generate stable thioethers. Testing revealed that pericosine A did not cause skin or eye irritation and was highly effective at deodorizing skunk anal gland secretions when formulated to include adjunctive cosmetic ingredients.
• 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.