barekoxide | 145458-09-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 环氧化物
• 英文名称: barekoxide
• 英文别名: (1S,2S,7S,10S,12R,14S)-2,6,6,10,14-pentamethyl-13-oxatetracyclo[8.6.0.02,7.012,14]hexadecane
• CAS: 145458-09-9
• 化学式: C₂₀H₃₄O
• 分子量: 290.489
• InChiKey: XLDXFKILDJRZEE-UXTPAWKISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  barekoxide 在 臭氧 作用下， 以 氘代氯仿 、 二氯甲烷 为溶剂， 反应 336.01h， 生成 (4aS,6aS,8R,11aS,11bS)-8-Hydroxy-4,4,6a,11b-tetramethyl-tetradecahydro-cyclohepta[a]naphthalen-9-one
  参考文献：
  名称：

  Asmarines G and H and Barekol, Three New Compounds from the Marine Sponge Raspailia sp.

  摘要：

  Four asmarines, the known A and F and two new ones G and H, four diterpenes, the known chelodane, barekoxide, and zaatirin and a new one, barekol, and methyl 3-oxo-cholan-24-oate were isolated from the Kenyan sponge Raspailia sp. The structures of all these compounds were established on the basis of MS and NMR data, and the absolute configuration of barekol was determined from the CD measurements of its keto-derivative. The N-15 chemical shifts of the N atoms of the heterocycles of the asmarines were measured from N-15 HMBC experiments, and the influence of various structural features on the delta(N) values studied.

  DOI：

  10.1021/np030261x
• 作为产物：
  描述：

  (4aS,6aS,8S,11aS,11bS)-4,4,6a,11b-tetramethyl-9-methylenetetradecahydro-1H-cyclohepta[a]naphthalen-8-ol 在 三乙基硅烷 、 三(五氟苯基)硼烷 、 间氯过氧苯甲酸 作用下， 以 1,2-二氯乙烷 、 二氯甲烷 为溶剂， 反应 15.0h， 以16.4 mg的产率得到barekoxide
  参考文献：
  名称：

  催化剂控制的正式 [4 + 3] 环加成应用于 (+)-Barekoxide 和 (-)-Barekol 的全合成

  摘要：

  双环二烯和硅氧基乙烯基重氮乙酸酯之间的串联环丙烷化/Cope 重排，由二铑催化剂 Rh(2)(R-PTAD)(4) 催化，有效地实现了对映发散 [4 + 3] 环加成。该反应通过环丙烷化和所得二乙烯基环丙烷的Cope重排进行。该方法用于合成 (+)-barekoxide (1) 和 (-)-barekol (2)。

  DOI：

  10.1021/ja103916t

文献信息

• 3-Bromobarekoxide, an unusual diterpene from Laurencia luzonensis
  作者：Masayuki Kuniyoshi、Mong S. Marma、Tatsuo Higa、Gérald Bernardinelli、Charles W. Jefford

  DOI：10.1039/b002530p

  日期：——

  A new, rare diterpene characterized by a cycloheptane ring trans-fused to a trans-decalin moiety was isolated from Laurencia luzonensis and its absolute structure determined by X-ray crystallography.

  从 Laurencia luzonensis 中分离出一种新的稀有二萜，其特征在于环庚烷环与反式萘烷部分融合，并通过 X 射线晶体学确定其绝对结构。
• Total Synthesis of the Diterpenes (+)-Randainin D and (+)-Barekoxide via Photoredox-Catalyzed Deoxygenative Allylation
  作者：Oleksandr Vyhivskyi、Olivier Baudoin

  DOI：10.1021/jacs.4c02224

  日期：——

  We report the first enantioselective total synthesis of diterpenoid randainin D, which possesses a hydroazulenone core with a β-substituted butenolide moiety on the cycloheptane ring. The trans-5/7 ring system was formed via a highly challenging ring-closing metathesis delivering the tetrasubstituted cycloheptenone. The butenolide moiety was installed via a novel deoxygenative allylation under Ir-photoredox

  我们报道了二萜 randainin D 的第一个对映选择性全合成，它具有氢薁酮核心，环庚烷环上有 β-取代的丁烯内酯部分。反式-5/7环系统是通过极具挑战性的闭环复分解形成的，从而产生四取代的环庚烯酮。使用草酸甲酯作为 red/ox 标签，在 Ir-光氧化还原催化下通过新型脱氧烯丙基化安装丁烯酸内酯部分。此外，所开发的烯丙基化已成功用于(+)-barek盐的7步全合成。这项研究表明，这种脱氧烯丙基化方法是在天然产物合成中形成 Cq-C(sp 3 ) 键（Cq = 四元中心）的一种有前景的策略。
• New Bromoterpenes from the Red Alga<i> Laurencia </i><i>l</i><i>uzonensis</i>
  作者：Masayuki Kuniyoshi、Mong S. Marma、Tatsuo Higa、Gérald Bernardinelli、Charles W. Jefford

  DOI：10.1021/np000638o

  日期：2001.6.1

  Extraction of a sample of Laurencia luzonensis collected off the coast of Kudaka Island, Okinawa, yielded the known sesquiterpenes palisol (1), palisadin B (2), palisadin A (3), pacifigorgiol (4), and aplysistatin (5), together with five new bromosesquiterpenes, isopalisol (6), luzonensol (7), luzonensol acetate (8), luzonensin (9), and (3Z,6E)-1-bromo-2-hydroxy-3,7,11-trimethyldodeca-3,6,10-triene (10). In addition, a new bromoditerpene of unusual structure, 3-bromobarekoxide (11), possessing a seven-membered ring fused to trans-decalin, was isolated.
• Catalyst-Controlled Formal [4 + 3] Cycloaddition Applied to the Total Synthesis of (+)-Barekoxide and (−)-Barekol
  作者：Yajing Lian、Laura C. Miller、Stephen Born、Richmond Sarpong、Huw M. L. Davies

  DOI：10.1021/ja103916t

  日期：2010.9.8

  dienes and siloxyvinyldiazoacetate, catalyzed by the dirhodium catalyst Rh(2)(R-PTAD)(4), effectively accomplishes enantiodivergent [4 + 3] cycloadditions. The reaction proceeds by a cyclopropanation followed by a Cope rearrangement of the resulting divinylcyclopropane. This methodology was applied to the synthesis of (+)-barekoxide (1) and (-)-barekol (2).

  双环二烯和硅氧基乙烯基重氮乙酸酯之间的串联环丙烷化/Cope 重排，由二铑催化剂 Rh(2)(R-PTAD)(4) 催化，有效地实现了对映发散 [4 + 3] 环加成。该反应通过环丙烷化和所得二乙烯基环丙烷的Cope重排进行。该方法用于合成 (+)-barekoxide (1) 和 (-)-barekol (2)。
• Asmarines G and H and Barekol, Three New Compounds from the Marine Sponge <i>Raspailia</i> sp.
  作者：Amira Rudi、Hagit Shalom、Michael Schleyer、Yehuda Benayahu、Yoel Kashman

  DOI：10.1021/np030261x

  日期：2004.1.1

  Four asmarines, the known A and F and two new ones G and H, four diterpenes, the known chelodane, barekoxide, and zaatirin and a new one, barekol, and methyl 3-oxo-cholan-24-oate were isolated from the Kenyan sponge Raspailia sp. The structures of all these compounds were established on the basis of MS and NMR data, and the absolute configuration of barekol was determined from the CD measurements of its keto-derivative. The N-15 chemical shifts of the N atoms of the heterocycles of the asmarines were measured from N-15 HMBC experiments, and the influence of various structural features on the delta(N) values studied.