humulene 9,10-epoxide | 21624-36-2

• 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: humulene 9,10-epoxide
• 英文别名: humulene epoxide III；humulene 9,10-oxide；(1S,3E,7E,11S)-3,7,10,10-tetramethyl-12-oxabicyclo[9.1.0]dodeca-3,7-diene
• CAS: 21624-36-2；69880-55-3；73951-53-8；87205-68-3
• 化学式: C₁₅H₂₄O
• 分子量: 220.355
• InChiKey: WSIKWSKUPSHZMF-ODEKHORNSA-N

物化性质

• 沸点：
  294.9±29.0 °C(Predicted)
• 密度：
  0.896±0.06 g/cm3(Predicted)
• LogP：
  4.944 (est)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  humulene 9,10-epoxide 在 platinum(IV) oxide potassium fluoride 、 三氟甲磺酸三甲基硅酯 、 氢气 、 sodium 、 三溴化磷 、 间氯过氧苯甲酸 、 lithium diisopropyl amide 作用下， 以 乙醚 、 二氯甲烷 、 氨 、 乙酸乙酯 为溶剂， 反应 36.67h， 生成 (+)-非洲醇
  参考文献：
  名称：

  hu草烯9,10-环氧化物的构象选择性跨环环化。两种骨架不同的环类hu草化合物的合成：dl-双环hu草烯酮和dl-非洲烷醇

  摘要：

  两个cyclohumulanoids，DL-bicyclohumulenone（ ）和DL-africanol（是通过葎草烯-9,10-环氧化物的新开发的构象上的选择性环化跨环（合成），该环氧化物转化成一个bicyclohumulenediol二乙酸酯中70％的产率通过用BF 3 · OET 2 -Ac 2 O，而治疗的三甲基甲硅烷三氟甲给了一个africen-10醇（a和收率80％b）。这两个中间体和提供的天然产物和从在30和8％的产率分别。

  DOI：

  10.1016/0040-4039(80)80152-3
• 作为产物：
  描述：

  Humulen-trioxid 在 正丁基锂 、 六氯化钨 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 以57%的产率得到humulene 9,10-epoxide
  参考文献：
  名称：

  Hydrolysis and reversible isomerization of humulene epoxides II and III.

  摘要：

  The hydrolysis reactions of humulene epoxide II (3) and humulene epoxide III (4) were studied in aqueous solution at pH 4.0. Twelve compounds from the hydrolysis of humulene epoxide II and 16 from humulene epoxide III were separated and identified. All of the compounds identified from hydrolysis of 3 also were found among the hydrolysis products of 4. A reversible transformation between these two epoxides proceeding through a bicyclic diol (15) as intermediate is responsible for producing the same products. Hydrolysis reactions further yielded diols and a number of different ring systems. The apparent intermediacy of carbocations also led to several elimination reaction products. Among the products identified from these epoxides, six have not been reported before. These are 1,5,8,8-tetramethyl-12-oxa-5-tricyclo[7.2.1.0(6,9)]dodecene (1), 4,8,11,11-tetramethyl-8-tricyclo-[7.2.0.0(2,5)]undecen-4-ol (5), stereoisomers of 2,6,6,9-tetramethyltricyclo[6.3.0.0(2,4)]undecane-5,9-diol (10, 14), 1,5,8,8-tetramethyl-8-bicyclo[8.1.0]undecene-2,9-diol (15), and the stereoisomeric pair 4,8,11,11-tetramethyl-tricyclo[6.3.0.0(2,4)]undecane-5,9-diol (16).

  DOI：

  10.1021/jo00043a033

文献信息

• Trimethysilyl triflate in organic synthesis11Part 11 of this series. Part 10: S. Murata and R. Noyori, Tetrahedron Letters 2107 (1981).
  作者：R. Noyori、S. Murata、M. Suzuki

  DOI：10.1016/s0040-4020(01)93263-6

  日期：——

  Trimethylsilyl triflate is a powerful silylating agent for organic compounds and acts as a catalyst which accelerates a variety of nucleophilic reactions in aprotic media. The reactions proceed via one-center, electrophilic coordination of the silyl group to hetero functional groups and exhibit unique selectivities.

  三氟甲磺酸三甲基甲硅烷基酯是有机化合物的强大甲硅烷基化剂，并充当催化剂，可加速非质子介质中的各种亲核反应。反应通过甲硅烷基与杂官能团的单中心亲电配位进行，并表现出独特的选择性。
• Stereochemical characterisation of the non-canonical α-humulene synthase from <i>Acremonium strictum</i>
  作者：Houchao Xu、Carsten Schotte、Russell J. Cox、Jeroen S. Dickschat

  DOI：10.1039/d1ob01769a

  日期：——

  α-humulene synthase was investigated through isotopic labelling experiments for its stereochemical course regarding inversion or retention at C-1, the face selectivity at C-11, and the stereoselectivity of the final deprotonation. A new and convenient desymmetrisation strategy was developed to enable a full stereochemical analysis of the catalysed steps to the achiral α-humulene product from stereoselectively

  通过同位素标记实验研究了非经典真菌 α-葎草烯合酶的立体化学过程，包括 C-1 处的反转或保留、C-11 处的面选择性以及最终去质子化的立体选择性。开发了一种新的、方便的去对称策略，能够对立体选择性标记的法尼基二磷酸酯生成非手性 α-葎草烯产物的催化步骤进行全面的立体化学分析。
• Hydrolysis and reversible isomerization of humulene epoxides II and III.
  作者：Xiaogen Yang、Max L. Deinzer

  DOI：10.1021/jo00043a033

  日期：1992.8

  The hydrolysis reactions of humulene epoxide II (3) and humulene epoxide III (4) were studied in aqueous solution at pH 4.0. Twelve compounds from the hydrolysis of humulene epoxide II and 16 from humulene epoxide III were separated and identified. All of the compounds identified from hydrolysis of 3 also were found among the hydrolysis products of 4. A reversible transformation between these two epoxides proceeding through a bicyclic diol (15) as intermediate is responsible for producing the same products. Hydrolysis reactions further yielded diols and a number of different ring systems. The apparent intermediacy of carbocations also led to several elimination reaction products. Among the products identified from these epoxides, six have not been reported before. These are 1,5,8,8-tetramethyl-12-oxa-5-tricyclo[7.2.1.0(6,9)]dodecene (1), 4,8,11,11-tetramethyl-8-tricyclo-[7.2.0.0(2,5)]undecen-4-ol (5), stereoisomers of 2,6,6,9-tetramethyltricyclo[6.3.0.0(2,4)]undecane-5,9-diol (10, 14), 1,5,8,8-tetramethyl-8-bicyclo[8.1.0]undecene-2,9-diol (15), and the stereoisomeric pair 4,8,11,11-tetramethyl-tricyclo[6.3.0.0(2,4)]undecane-5,9-diol (16).
• Conformationally selective transannular cyclizations of humulene 9,10-epoxide. Synthesis of the two skeletally different cyclohumulanoids: dl-bicyclohumulenone and dl-africanol
  作者：Haruhisa Shirahama、Kiyoharu Hayano、Yoshiro Kanemoto、Shunjiro Misumi、Toshikazu Ohtsuka、Nobuhiro Hashiba、Akio Furusaki、Shizuaki Murata、Ryoji Noyori、Takeshi Matsumoto

  DOI：10.1016/0040-4039(80)80152-3

  日期：1980.1

  Two cyclohumulanoids, dl-bicyclohumulenone () and dl-africanol ( were synthesized through newly developed conformationally selective transannular cyclization of humulene 9,10-epoxide (). The epoxide was converted to a bicyclohumulenediol diacetate in 70% yield by treatment with BF3·OEt2-Ac2O, while treatment of with trimethylsilyl trifluoromethansulfonate gave an africen-10-ol (a and b) in 80% yield

  两个cyclohumulanoids，DL-bicyclohumulenone（ ）和DL-africanol（是通过葎草烯-9,10-环氧化物的新开发的构象上的选择性环化跨环（合成），该环氧化物转化成一个bicyclohumulenediol二乙酸酯中70％的产率通过用BF 3 · OET 2 -Ac 2 O，而治疗的三甲基甲硅烷三氟甲给了一个africen-10醇（a和收率80％b）。这两个中间体和提供的天然产物和从在30和8％的产率分别。