(1R,2R,4aS,8aS)-1,2-epoxy-1-(hydroxymethyl)-2,5,5,8a-tetramethyldecahydronaphthalene | 137266-44-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: (1R,2R,4aS,8aS)-1,2-epoxy-1-(hydroxymethyl)-2,5,5,8a-tetramethyldecahydronaphthalene
• 英文别名: 8α,9α-epoxydriman-11-ol；(8aS)-α-epoxy bicyclofarnesol；11-hydroxydrim-8(9)-α-epoxide；[(1aR,3aS,7aS,7bR)-1a,4,4,7a-tetramethyl-2,3,3a,5,6,7-hexahydronaphtho[1,2-b]oxiren-7b-yl]methanol
• CAS: 137266-44-5；137331-32-9
• 化学式: C₁₅H₂₆O₂
• 分子量: 238.37
• InChiKey: DOCUUDXRCISUKY-MHEUCROKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  32.8
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,2R,4aS,8aS)-1,2-epoxy-1-(hydroxymethyl)-2,5,5,8a-tetramethyldecahydronaphthalene 在 chromium trioxide-pyridine complex 作用下， 生成 (+/-)-Drim-9(11)-en-8α-ol
  参考文献：
  名称：

  米曲霉drim-9（11）-en-8-ols的合成及绝对构型

  摘要：

  对映体合成的drimane倍半萜1和2已实现从二萜（+）-royleanone（3）通过其衍生物5。该结果证实，从米曲霉分离的天然倍半萜具有类固醇一样的正常绝对立体化学。这个结论与最近发表的其他数据相反。

  DOI：

  10.1016/s0040-4039(00)92302-5
• 作为产物：
  描述：

  (1R,2R,4aS,8aS)-(+)-2-hydroxy-1,2,3,4,4a,5,6,7,8,8a-decahydro-2,5,5,8a-tetramethyl-naphthalen-1-aldehyde 在 sodium tetrahydroborate 、 单过氧邻苯二甲酸 、 碘 作用下， 以 乙醚 、 乙醇 、 苯 为溶剂， 反应 4.0h， 生成 (1R,2R,4aS,8aS)-1,2-epoxy-1-(hydroxymethyl)-2,5,5,8a-tetramethyldecahydronaphthalene
  参考文献：
  名称：

  对南多烷骨架的进一步合成研究：南多烷的合成

  摘要：

  austrodoral (1) 是一种海洋去甲倍半萜，含有独特的双环骨架，已实现合成。合成策略基于从市售 (+)-sclareolide (4) 获得的合适的光学活性 drimanic 环氧衍生物的环收缩。发现氟磺酸有效地促进环收缩。去甲倍半萜烃 13 是合成倍半萜对苯二酚的关键中间体，也已制备成旋光形式。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

  DOI：

  10.1002/ejoc.200400795

文献信息

• Lead(IV) acetate mediated cleavage of β-hydroxy ethers: enantioselective synthesis of α-acetoxy carbonyl compounds
  作者：Enrique Alvarez-Manzaneda、Rachid Chahboun、Esteban Alvarez、Ramón Alvarez-Manzaneda、Pedro E. Muñoz、Fermín Jimenez、Hanane Bouanou

  DOI：10.1016/j.tet.2011.09.056

  日期：2011.11

  α-Acetoxy aldehydes or α-acetoxy ketones can be efficiently synthesized by treating 2,3-epoxy primary alcohols with lead tetraacetate. The reaction, which proceeds with complete regio- and stereoselectivity facilitates the enantioselective synthesis of α-acetoxy carbonyl compounds from allyl alcohols, via Sharpless epoxidation. Cyclic β-hydroxy ethers, with an oxygenated five-, six- or seven-membered

  通过用四乙酸铅处理2，3-环氧伯醇可以有效地合成α-乙酰氧基醛或α-乙酰氧基酮。以完全的区域和立体选择性进行的反应有助于通过Sharpless环氧化由烯丙醇对映体选择性合成α-乙酰氧基羰基化合物。具有氧化的五元，六元或七元环的环状β-羟基醚被转化为α-乙酰氧基醚。
• Synthesis of Drim-9(11)-en-8α- and -8β-ols from Drimenol
  作者：K. I. Kuchkova、A. N. Aryku、I. P. Dragalin、P. F. Vlad

  DOI：10.1007/s10600-005-0109-8

  日期：2005.3

  Drim-9(11)-en-8α-ol and drim-9(11)-en-8β-ol were synthesized in six steps from drimenol. Drimenol was oxidized by P2O5 and DMSO to drimenal, which isomerized with p-TsOH into isodrimenal. Isodrimenal was reduced by NaBH4 into isodrimenol, epoxidation of which by m-CPBA gave a mixture (3.4:1) of α- and β-epoxyisodrimenols. These reacted with tosyl chloride in Py to give a mixture of α- and β-epoxyisodrimenol tosylates. Treatment of the tosylate mixture with KI and then Ph3P produced a mixture of drim-9(11)-en-8α- and -8β-ols that was separated chromatographically. The overall yield was ∼26%.

  Drim-9(11)-en-8α-醇和drim-9(11)-en-8β-醇是通过六个步骤从drimenol合成的。drimenol先由P2O5和DMSO氧化为drimenal，随后在p-TsOH的催化下异构化为isodrimenal。isodrimenal再通过NaBH4还原为isodrimenol，接着用m-CPBA进行环氧化，得到混合物(3.4:1)的α-和β-环氧isodrimenol。这些化合物与吡啶中的tosyl氯反应，生成α-和β-环氧isodrimenol tosylates的混合物。将该tosylate混合物与KI及Ph3P处理后，分离得到drim-9(11)-en-8α-和-8β-醇的混合物，通过色谱分离。这一系列反应的总体产率约为26%。
• Lead(IV) acetate oxidative ring-opening of 2,3-epoxy primary alcohols: a new entry to optically active α-hydroxy carbonyl compounds
  作者：Enrique Alvarez-Manzaneda、Rachid Chahboun、Esteban Alvarez、Ramón Alvarez-Manzaneda、Pedro E. Muñoz、Fermín Jiménez、Hanane Bouanou

  DOI：10.1016/j.tetlet.2011.05.116

  日期：2011.8

  The treatment of 2,3-epoxy primary alcohols with lead(IV) acetate (LTA) leads to α-acetoxy aldehydes or α-acetoxy ketones, through the nucleophilic ring-opening of an intermediate oxonium and the subsequent carbon–carbon bond cleavage. This reaction represents a new route to optically active α-hydroxy carbonyl compounds.

  通过中间体氧鎓的亲核开环和随后的碳-碳键裂解，用乙酸铅（IV）（LTA）处理2,3-环氧伯醇可产生α-乙酰氧基醛或α-乙酰氧基酮。该反应代表了制备旋光性α-羟基羰基化合物的新途径。
• Acid-Promoted Rearrangement of Drimane Type Epoxy Compounds and Their Application in Natural Product Synthesis
  作者：Naoko Fujiwara、Masako Kinoshita、Akira Uchida、Machiko Ono、Keisuke Kato、Hiroyuki Akita

  DOI：10.1248/cpb.60.562

  日期：——

  The reactions of (±)-α-epoxy drimenol (4) and (±)-α-epoxy drimenyl cyanide (6) with acids (proton acid or Lewis acid) selectively gave the rearranged aldehyde (±)-13 and (±)-15 having the hydroindane skeleton, respectively, while the reactions of (±)-4 and (±)-6 with Dibal-H selectively afforded the allyl alcohol (±)-14 and (±)-16, respectively. The reactions of (8aR)-6 and (8aS)-6 with Dibal-H were applied for the determination of the absolute structure of natural 7β-acetoxy-ent-labda-8(17),13(14)E-dien-15-ol (18). The reaction of (±)-α-epoxy bicyclofarnesol (5) and (8aS)-5 with proton acid selectively provided the rearranged ketol (±)- and (8aS)-31 having the hydroindane skeleton, respectively. The optically active (8aS)-31 was converted to the natural (9S)-austrodoric acid (33).

  (±)-α-环氧地美酚(4)和(±)-α-环氧地美酚氰(6)与酸(质子酸或路易斯酸)的反应分别选择性地得到了以氢茚为骨架的重排醛(±)-13和(±)-15，而(±)-4和(±)-6与Dibal-H的反应则分别选择性地得到了烯丙基醇(±)-14和(±)-16。(8aR)-6 和 (8aS)-6 与 Dibal-H 的反应被用于确定天然 7β-acetoxy-ent-labda-8(17),13(14)E-dien-15-ol (18) 的绝对结构。(±)-α-环氧双环法呢醇(5)和(8aS)-5 与质子酸的反应分别选择性地提供了具有氢茚满骨架的重排酮醇(±)-和(8aS)-31。具有光学活性的 (8aS)-31 被转化为天然的 (9S)-Austrodoric acid (33)。
• Enantiospecific, Biosynthetically Inspired Formal Total Synthesis of (+)-Liphagal
  作者：Jonathan H. George、Jack E. Baldwin、Robert M. Adlington

  DOI：10.1021/ol100756z

  日期：2010.5.21

  A biosynthetically inspired synthesis of (+)-liphagal has been achieved from (+)-sclareolide in 13 steps (9% overall yield). The key step is a biomimetic ring expansion of a highly stabilized benzylic carbocation, which generates the seven-membered ring and the benzofuran of the natural product in a single cascade reaction.