methyl (3aR,4R,7aR)-4-(((trifluoromethyl)sulfonyl)oxy)-3a,4,5,7a-tetrahydrospiro[benzo[d][1,3]dioxole-2,1'-cyclohexane]-6-carboxylate | 272123-64-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: methyl (3aR,4R,7aR)-4-(((trifluoromethyl)sulfonyl)oxy)-3a,4,5,7a-tetrahydrospiro[benzo[d][1,3]dioxole-2,1'-cyclohexane]-6-carboxylate
• 英文别名: methyl (3aR,7R,7aR)-7-(trifluoromethylsulfonyloxy)spiro[3a,6,7,7a-tetrahydro-1,3-benzodioxole-2,1'-cyclohexane]-5-carboxylate
• CAS: 272123-64-5
• 化学式: C₁₅H₁₉F₃O₇S
• 分子量: 400.373
• InChiKey: YBKWJKOOTYVFSC-IJLUTSLNSA-N

物化性质

• 沸点：
  446.3±45.0 °C(Predicted)
• 密度：
  1.47±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.17
• 重原子数：
  26.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  88.13
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  methyl (3aR,4R,7aR)-4-(((trifluoromethyl)sulfonyl)oxy)-3a,4,5,7a-tetrahydrospiro[benzo[d][1,3]dioxole-2,1'-cyclohexane]-6-carboxylate 在 cesium acetate 作用下， 以 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：

  乙二醛酶-I抑制剂COTC的新合成

  摘要：

  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。

  DOI：

  10.1016/s0040-4039(00)00103-9
• 作为产物：
  描述：

  莽草酸 在 吡啶 、 4-二甲氨基吡啶 、 D(+)-10-樟脑磺酸 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 3.75h， 生成 methyl (3aR,4R,7aR)-4-(((trifluoromethyl)sulfonyl)oxy)-3a,4,5,7a-tetrahydrospiro[benzo[d][1,3]dioxole-2,1'-cyclohexane]-6-carboxylate
  参考文献：
  名称：

  海洋天然产物（-）-Pericosine E的合成

  摘要：

  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。

  DOI：

  10.1021/ol501631r

文献信息

• 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.
• 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.