methyl (3aR,7aS)-3a,7a-dihydrospiro[benzo[d][1,3]dioxole-2,1'-cyclohexane]-5-carboxylate | 272123-66-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (3aR,7aS)-3a,7a-dihydrospiro[benzo[d][1,3]dioxole-2,1'-cyclohexane]-5-carboxylate
• 英文别名: methyl (3aR,7aS)-spiro[3a,7a-dihydro-1,3-benzodioxole-2,1'-cyclohexane]-5-carboxylate
• CAS: 272123-66-7
• 化学式: C₁₄H₁₈O₄
• 分子量: 250.295
• InChiKey: QVFBWTZXUZGAEI-NWDGAFQWSA-N

物化性质

• 沸点：
  367.2±42.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (3aR,7aS)-3a,7a-dihydrospiro[benzo[d][1,3]dioxole-2,1'-cyclohexane]-5-carboxylate 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 水 、 乙腈 为溶剂， 反应 3.0h， 以55%的产率得到methyl (3aR,4R,5S,7aR)-4-bromo-5-hydroxy-3a,4,5,7a-tetrahydrospiro[benzo[d][1,3]dioxole-2,1'-cyclohexane]-6-carboxylate
  参考文献：
  名称：

  天然O-连接的Carba-二糖，（+）-和（-）-Pericosine E的合成及其类似物作为α-葡萄糖苷酶抑制剂。

  摘要：

  Pericosine E（6）是Periconia byssoides OUPS-N133的代谢产物，最初是从海兔Aplysia kurodai中分离出来的，该菌在自然界中以对映体混合物的形式存在。使用普通的简单合成策略，已实现了Periconia byssoides OUPS-N133的两个对映体的对映体特异性合成，以及六个立体异构体。对于这些有效的合成，采用了高度区域选择性和立体选择性的方法来制备溴代醇和抗环氧中间体。为了获得独特的O-连接的二糖结构，使用催化的BF 3·Et 2 O实现了氯醇作为供体和抗环氧化物作为受体的偶联。大多数合成的化合物对来自酵母的α-糖苷酶表现出选择性显着的抑制活性。

  DOI：

  10.3390/md15010022
• 作为产物：
  描述：

  methyl shikimate 在 吡啶 、 4-二甲氨基吡啶 、 camphor-10-sulfonic acid 、 cesium acetate 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 methyl (3aR,7aS)-3a,7a-dihydrospiro[benzo[d][1,3]dioxole-2,1'-cyclohexane]-5-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 (−)-pericosine B, the antipode of the cytotoxic marine natural product
  作者：Yoshihide Usami、Kentaro Suzuki、Koji Mizuki、Hayato Ichikawa、Masao Arimoto

  DOI：10.1039/b813072h

  日期：——

  The stereoselective synthesis of (−)-pericosine B, which is the antipode of the cytotoxic metabolite of the fungus Periconia byssoides OUPS-N133 separated from the sea hare, was accomplished in 9 steps in 12% total yield from (−)-quinic acid, together with the synthesis of its epimer. Every crucial step of this total synthesis, including ring opening of a β-epoxide and NaBH4reduction of an unstable

  与海兔分离的真菌（Periconia byssoides OUPS-N133）的细胞毒性代谢产物的对映体（-）-pericosine B的立体选择性合成以9步完成，从（-）-奎宁酸的总收率为12％ ，连同其差向异构体的合成。整个合成过程中的每个关键步骤，包括β-环氧化物的开环和不稳定的β，γ-不饱和烯酮的NaBH 4还原，都具有出色的立体选择性。
• 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。
• A new synthesis of the glyoxalase-I inhibitor COTC
  作者：C.Frederick M Huntley、Harold B Wood、Bruce Ganem

  DOI：10.1016/s0040-4039(00)00103-9

  日期：2000.3

  A stereoselective, chiral synthesis of the glyoxalase I inhibitor 2-crotonyloxymethyl-(4R,5R,6R)-4,5,6-trihydroxycyclohex-2-enone 1 (COTC) from a simple derivative of (−)-quinic acid is described.

  乙二醛酶I抑制剂2-巴豆酰氧基甲基-（4 R，5 R，6 R）-4,5,6-三羟基环己基-2-烯酮1（COTC）的立体选择性手性合成是由（-）-奎尼奇的简单衍生物形成的描述了酸。
• Microwave-Aided One-Pot Dehydration of the Alcohol Derived from (−)-Shikimic Acid for Efficient Synthesis of Pericosines
  作者：Yoshihide Usami、Koji Mizuki、Yusuke Yoneshige、Rikiya Kawahata、Hiroki Yoneyama、Shinya Harusawa

  DOI：10.3987/com-14-13053

  日期：——

  Dehydrating conditions of shikimate-derived alcohol 7, an early intermediate in the synthesis of the pericosine family of marine natural products, were examined. The triflate 8 was effectively converted to cyclohexadiene 9 with excess 4-N,N-dimethylaminopyridine (DMAP) at room temperature for 24 h. The reaction time was dramatically shortened by heating under microwave (MW) irradiation, preventing formation of the Diels-Alder type byproduct 14. Furthermore, the MW-aided one-pot dehydration of alcohol 7 with Tf2O and DMAP (2.4 eq.) to form diene 9 was realized.