ent-16-beyeran-16-one | 40140-46-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: ent-16-beyeran-16-one
• 英文别名: ent-Beyeran-16-on；(1R,4R,9R,10R,13S)-5,5,9,13-tetramethyltetracyclo[11.2.1.01,10.04,9]hexadecan-14-one
• CAS: 40140-46-3
• 化学式: C₂₀H₃₂O
• 分子量: 288.473
• InChiKey: PVGAAHIWPVFYJG-OPTDIUSFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  ent-16-beyeran-16-one 在 吡啶 、 盐酸羟胺 作用下， 反应 20.0h， 以92%的产率得到ent-16-beyeran-16-one oxime
  参考文献：
  名称：

  16-Aza-ent-beyerane and 16-Aza-ent-trachylobane:  Potent Mechanism-Based Inhibitors of Recombinant ent-Kaurene Synthase from Arabidopsis thaliana

  摘要：

  The secondary ent-beyeran-16-yl carbocation (7) is a key branch point intermediate in mechanistic schemes to rationalize the cyclic structures of many tetra- and pentacyclic diterpenes, including ent-beyerene, ent-kaurene, ent-trachylobane, and ent-atiserene, presumed precursors to >1000 known diterpenes. To evaluate these mechanistic hypotheses, we synthesized the heterocyclic analogues 16-aza-ent-beyerane (12) and 16-aza-ent-trachylobane (13) by means of Hg(Il)- and Pb(IV)-induced cyclizations onto the A12 double bonds of tricyclic intermediates bearing carbamoylmethyl and aminomethyl groups at C-8. The 13,16-seco-16-norcarbamate (20a) was obtained from ent-beyeran-16-one oxime (17) by Beckmann fragmentation, hydrolysis, and Curtius rearrangement. The aza analogues inhibited recombinant ent-kaurene synthase from Arabidopsis thaliana (GST-rAtKS) with inhibition constants (IC50 = 1 X 10(-7) and 1 X 10(-6) M) similar in magnitude to the pseudo-binding constant of the bicyclic ent-copalyl cliphosphate substrate (K-m = 3 x 10-7 M). Large enhancements of binding affinities (ICK = 4 x 10(-9) and 2 x 10(-8) M) were observed in the presence of 1 mM pyrophosphate, which is consistent with a tightly bound ent-beyeranyl(+)/ pyrophosphate- ion pair intermediate in the cyclization -rearrangement catalyzed by this diterpene synthase. The weak inhibition (IC50 = 1 x 10(-5) M) exhibited by ent-beyeran-16-exo-yl diphosphate (111) and its failure to undergo bridge rearrangement to kaurene appear to rule out the covalent cliphosphate as a free intermediate. 16-Aza-ent-beyerane is proposed as an effective mimic for the ent-beyeran-1 6-yl carbocation with potential applications as an active site probe for the various ent-diterpene cyclases and as a novel, selective inhibitor of gibberellin biosynthesis in plants.

  DOI：

  10.1021/ja072447e
• 作为产物：
  描述：

  (+)-hibaene 在 chromium(VI) oxide 、 硫酸 作用下， 反应 2.0h， 生成 ent-16-beyeran-16-one
  参考文献：
  名称：

  Bowen,D.H. et al., Journal of the Chemical Society. Perkin transactions I, 1975, p. 378 - 382

  摘要：

  DOI：

文献信息

• Ring C Functionalized Diterpenoids. Part III. 12-Substituted <i>ent</i>-Beyeranes
  作者：John Cairns Fairlie、Alan James McAlees、Robert McCrindle、Eli Neidert

  DOI：10.1139/v74-111

  日期：1974.3.1

  On treatment with hot formic acid ent-16-kaurene (4a) and the related ester 4b give a mixture containing 12-, 15- and 16-ent-beyerane derivatives (10a, 1a; 7a, 12a; 9a, 11a) in which the last predominates, while ent-15-beyerene (5a) gives mainly the C-15 formate 7a. In keeping with the anticipated longer lifetimes of the intermediate ions 2 and 3 in trifluoroacetic acid as compared with formic acid

  用热甲酸 ent-16-kaurene (4a) 和相关酯 4b 处理，得到含有 12-、15- 和 16-ent-beyerane 衍生物（10a, 1a; 7a, 12a; 9a, 11a）的混合物，其中最后一个占主导地位，而 ent-15-beyerene (5a) 主要产生 C-15 甲酸盐 7a。与甲酸相比，三氟乙酸中中间离子 2 和 3 的预期寿命更长，4b 在前一种介质中在室温下反应得到含有 1c、11c 和 12c 的混合物，其中的相对产率是12-取代衍生物（1c）显着增加。在相同条件下处理 ent-trachyloban-19-oate 甲酯 (14) 或 ent-15-atisen-19-oate 甲酯 (6b) 得到与 4b 相似的混合物。
• Bowen,D.H. et al., Journal of the Chemical Society. Perkin transactions I, 1975, p. 378 - 382
  作者：Bowen,D.H. et al.

  DOI：——

  日期：——
• 16-Aza-<i>ent</i>-beyerane and 16-Aza-<i>ent</i>-trachylobane:  Potent Mechanism-Based Inhibitors of Recombinant <i>ent</i>-Kaurene Synthase from <i>Arabidopsis thaliana</i>
  作者：Arnab Roy、Frank G. Roberts、P. Ross Wilderman、Ke Zhou、Reuben J. Peters、Robert M. Coates

  DOI：10.1021/ja072447e

  日期：2007.10.1

  The secondary ent-beyeran-16-yl carbocation (7) is a key branch point intermediate in mechanistic schemes to rationalize the cyclic structures of many tetra- and pentacyclic diterpenes, including ent-beyerene, ent-kaurene, ent-trachylobane, and ent-atiserene, presumed precursors to >1000 known diterpenes. To evaluate these mechanistic hypotheses, we synthesized the heterocyclic analogues 16-aza-ent-beyerane (12) and 16-aza-ent-trachylobane (13) by means of Hg(Il)- and Pb(IV)-induced cyclizations onto the A12 double bonds of tricyclic intermediates bearing carbamoylmethyl and aminomethyl groups at C-8. The 13,16-seco-16-norcarbamate (20a) was obtained from ent-beyeran-16-one oxime (17) by Beckmann fragmentation, hydrolysis, and Curtius rearrangement. The aza analogues inhibited recombinant ent-kaurene synthase from Arabidopsis thaliana (GST-rAtKS) with inhibition constants (IC50 = 1 X 10(-7) and 1 X 10(-6) M) similar in magnitude to the pseudo-binding constant of the bicyclic ent-copalyl cliphosphate substrate (K-m = 3 x 10-7 M). Large enhancements of binding affinities (ICK = 4 x 10(-9) and 2 x 10(-8) M) were observed in the presence of 1 mM pyrophosphate, which is consistent with a tightly bound ent-beyeranyl(+)/ pyrophosphate- ion pair intermediate in the cyclization -rearrangement catalyzed by this diterpene synthase. The weak inhibition (IC50 = 1 x 10(-5) M) exhibited by ent-beyeran-16-exo-yl diphosphate (111) and its failure to undergo bridge rearrangement to kaurene appear to rule out the covalent cliphosphate as a free intermediate. 16-Aza-ent-beyerane is proposed as an effective mimic for the ent-beyeran-1 6-yl carbocation with potential applications as an active site probe for the various ent-diterpene cyclases and as a novel, selective inhibitor of gibberellin biosynthesis in plants.