methyl (3R,4S,5R,6S)-6-chloro-3,4-O-cyclohexylidene-3,4,5-trihydroxy-1-cyclohexene-1-carboxylate | 1054623-17-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (3R,4S,5R,6S)-6-chloro-3,4-O-cyclohexylidene-3,4,5-trihydroxy-1-cyclohexene-1-carboxylate
• 英文别名: methyl (3aS,4S,7R,7aS)-4-chloro-7-hydroxy-3a,4,7,7a-tetrahydrospiro[benzo[d][1,3]dioxole-2,1'-cyclohexane]-5-carboxylate；methyl (3aS,4S,7R,7aS)-4-chloro-7-hydroxyspiro[3a,4,7,7a-tetrahydro-1,3-benzodioxole-2,1'-cyclohexane]-5-carboxylate
• CAS: 1054623-17-4
• 化学式: C₁₄H₁₉ClO₅
• 分子量: 302.755
• InChiKey: XGYILYAZRVUZKL-NOOOWODRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  20
• 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 (3R,4S,5R,6S)-6-chloro-3,4-O-cyclohexylidene-3,4,5-trihydroxy-1-cyclohexene-1-carboxylate 在 三氟乙酸 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以96%的产率得到pericosine Do
  参考文献：
  名称：

  立体构象的重新分配和Pericosine D o的绝对构型的合成方法测定

  摘要：

  化学合成和NMR方法的组合被用来重新分配percosine D o（8）的结构，percosine D o（8）是一种由真菌Periconia byssoides OUPS-N133产生的具有细胞毒性的海洋天然产物，最初源自海兔Aplysia kurodai。化学合成被用来从已知的氯醇制备pericoisne D o（8），而后者又衍生自（-）-奎宁酸。天然pericosine d的绝对构型Ô（8测定）为甲基（3- [R，4小号，5小号，6小号）-6-氯-3,4,5-三羟基-1-环己烯-1-羧酸酯。HPLC分析使用手性相柱表明pericosine d Ô（8）存在于自然界中的对映体纯的形式。

  DOI：

  10.1021/np100843j
• 作为产物：
  描述：

  methyl shikimate 在 吡啶 、 盐酸 、 4-二甲氨基吡啶 、 oxone 、 camphor-10-sulfonic acid 、 cesium acetate 、 碳酸氢钠 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 生成 methyl (3R,4S,5R,6S)-6-chloro-3,4-O-cyclohexylidene-3,4,5-trihydroxy-1-cyclohexene-1-carboxylate
  参考文献：
  名称：

  An Electrophilic Natural Product Provides a Safe and Robust Odor Neutralization Approach To Counteract Malodorous Organosulfur Metabolites Encountered in Skunk Spray

  摘要：

  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.

  DOI：

  10.1021/acs.jnatprod.9b00415

文献信息

• 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。
• Stereostructure Reassignment and Determination of the Absolute Configuration of Pericosine D_o by a Synthetic Approach
  作者：Yoshihide Usami、Koji Mizuki

  DOI：10.1021/np100843j

  日期：2011.4.25

  reassign the structure of pericosine Do (8), a cytotoxic marine natural product produced by the fungus Periconia byssoides OUPS-N133 that was originally derived from the sea hare Aplysia kurodai. Chemical synthesis was used to prepare pericoisne Do (8) from a known chlorohydrin that was in turn derived from (−)-quinic acid. The absolute configuration of natural pericosine Do (8) was determined to be

  化学合成和NMR方法的组合被用来重新分配percosine D o（8）的结构，percosine D o（8）是一种由真菌Periconia byssoides OUPS-N133产生的具有细胞毒性的海洋天然产物，最初源自海兔Aplysia kurodai。化学合成被用来从已知的氯醇制备pericoisne D o（8），而后者又衍生自（-）-奎宁酸。天然pericosine d的绝对构型Ô（8测定）为甲基（3- [R，4小号，5小号，6小号）-6-氯-3,4,5-三羟基-1-环己烯-1-羧酸酯。HPLC分析使用手性相柱表明pericosine d Ô（8）存在于自然界中的对映体纯的形式。
• Determination of the absolute configuration of the cytotoxic natural product pericosine D
  作者：Yoshihide Usami、Koji Mizuki、Hayato Ichikawa、Masao Arimoto

  DOI：10.1016/j.tetasy.2008.06.008

  日期：2008.6

  The synthesis of two diastereomers of pericosine A from (-)-quinic acid was achieved, thus enabling the confirmation of the relative configuration and elucidation of the absolute stereochemistry of cytotoxic natural product pericosine D assigned as methyl (3R,4R,5S,6R)-6-chloro-3,4,5-trihydroxy-1-cyclohexene-1-carboxylate. (C) 2008 Elsevier Ltd. All rights reserved.
• 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.