β-chamigrene | 87935-44-2

• 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: β-chamigrene
• 英文别名: (+)-beta-Chamigrene；(6S)-5,5,9-trimethyl-1-methylidenespiro[5.5]undec-9-ene
• CAS: 87935-44-2
• 化学式: C₁₅H₂₄
• 分子量: 204.356
• InChiKey: WLNGPDPILFYWKF-HNNXBMFYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  15
• 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：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  deschloroelatol 在 吡啶 、 三乙基硼氢化锂 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 β-chamigrene
  参考文献：
  名称：

  对映选择性环构建：卤化海洋天然螺[5.5]十一烷倍半萜的合成

  摘要：

  本研究的主要目标是开发一种通用方法，以在溴鎓引发的分子内碳环化反应中实现大量的不对称诱导。该目标已通过生成包含位于环己烯环上的两个立体原原子的环外亚烷基来实现。该过程的立体化学已经进行了一些详细的研究，并且全合成 (-)-(2R,6S,8S,9S)-2,8-dibromo-9-hydroxy-cr-chamigrene (9) , (- )-(2R,6S,8S,9S)-2,8-dibromo-9-hydroxy-fl-chamigrene (lo), (-)-(2R,6S)-2-bromo-fl-chamigrene (5), (-)-P-chamigrene (6) 及其相应的 (+)-11、-12、-7 和 -8 对映异构体首次被描述。这些化合物由 (8S,9S)-8-bromo-9-hydroxy-(E)-y-bisabolene、(-)-33 和 (8R,9R)-8-bromo-9

  DOI：

  10.1021/ja00284a052

文献信息

• Catalytic Asymmetric Spirocyclizing Diels–Alder Reactions of Enones: Stereoselective Total and Formal Syntheses of α-Chamigrene, β-Chamigrene, Laurencenone C, Colletoic Acid, and Omphalic Acid
  作者：Santanu Ghosh、Johannes Eike Erchinger、Rajat Maji、Benjamin List

  DOI：10.1021/jacs.2c01971

  日期：2022.4.20

  We disclose a general catalytic enantioselective Diels–Alder reaction of exo-enones with dienes to give spirocyclanes. The obtained products feature highly congested quaternary stereogenic spirocenters and are used in concise total and formal syntheses of several sesquiterpenes, including of α-chamigrene, β-chamigrene, laurencenone C, colletoic acid, and omphalic acid. The stereo- and regioselectivities

  我们公开了外烯酮与二烯的一般催化对映选择性 Diels-Alder 反应生成螺环烷。获得的产品具有高度拥挤的四元立体螺中心，可用于几种倍半萜烯的简明全合成和正式合成，包括α-chamigrene、β-chamigrene、月桂烯酮 C、colletoic 酸和 omphalic 酸。我们的螺环化环加成反应的立体选择性和区域选择性受到强酸性和受限的亚氨基二亚磷酸酯催化剂的有效控制。计算研究揭示了反应性和选择性的起源。
• Stereochemical features of sesquiterpene metabolites as a distinctive trait of red seaweeds in the genus Laurencia
  作者：Graziano Guella、Aysel Öztunç、Ines Mancini、Francesco Pietra

  DOI：10.1016/s0040-4039(97)10162-9

  日期：1997.11

  Red seaweeds in the genus Laurencia may be classified into four lineages according to the stereochemical features of their metabolites, i.e. the known obtusane (like obtusol (+)-1), isoobtusane (like isoobtusol (+)-2) and rogiolane (like rogiolol (−)-3) and — structurally revised and renamed here — cartilagineane chamigrene sesquiterpenes (like cartilagineol 10), in a vision that encompasses also biogenetic

  根据其代谢产物的立体化学特征，Laurencia属中的红海藻可分为四个谱系，即已知的ob丁烷（如obtusol（+）- 1），异obtusane（如isoobtusol（+）- 2）和rogiolane（如rogiolol）。 （−）- 3），以及-在结构上进行了修订并重命名的-软骨素倍半萜烯倍半萜烯（如软骨素10），这一愿景还涵盖了诸如环戊倍半萜烯等生物遗传后代，并符合历史偶然性的观念。
• Two sesquiterpene synthases are responsible for the complex mixture of sesquiterpenes emitted from Arabidopsis flowers
  作者：Dorothea Tholl、Feng Chen、Jana Petri、Jonathan Gershenzon、Eran Pichersky

  DOI：10.1111/j.1365-313x.2005.02417.x

  日期：2005.4

  Despite the fact that Arabidopsis is largely self‐pollinating, its flowers emit a complex mixture of terpene volatiles consisting predominantly of a large group of over 20 sesquiterpenes. Here we report that only two terpene synthases, encoded by the florally expressed genes At5g23960 and At5g44630, are responsible for the formation of virtually all sesquiterpenes found in the Arabidopsis floral volatile blend. Two independent mutant lines with T‐DNA insertions in the previously identified At5g23960 gene lacked the emission of three sesquiterpenes, including the main sesquiterpene volatile (E)‐β‐caryophyllene, confirming the previous in vitro functional assignment for this gene. Flowers of a mutant line carrying a T‐DNA insertion in gene At5g44630 emitted these three sesquiterpenes, but did not emit any of the remaining sesquiterpene volatiles. An At5g44630 cDNA was expressed in Escherichia coli and the produced protein catalyzed the conversion of farnesyl diphosphate into over 15 sesquiterpenes in similar proportions to those found in the floral volatile blend. At5g23960 and At5g44630 promoter‐β‐glucuronidase (GUS) fusion experiments demonstrated that both genes are expressed in several parts of the Arabidopsis flower, with strong At5g23960 promoter‐GUS activity in the stigma and strong expression of At5g44630 in intrafloral nectaries. Given the previously reported antimicrobial activity of terpenes, their production in stigmas and nectaries may serve to inhibit microbial infection at these vulnerable sites. A survey of 37 Arabidopsis thaliana ecotypes revealed quantitative, but almost no qualitative, variations of floral monoterpene and sesquiterpene emissions suggesting that floral terpene volatiles must play some significant role in the life of the Arabidopsis plant.

  摘要尽管拟南芥在很大程度上是自花授粉的，但它的花却能散发出复杂的萜烯挥发物混合物，主要由 20 多种倍半萜组成。在这里，我们报告了只有两个萜烯合成酶（由花卉表达基因 At5g23960 和 At5g44630 编码）负责拟南芥花卉挥发性混合物中几乎所有倍半萜的形成。在先前确定的 At5g23960 基因中插入 T-DNA 的两个独立突变株缺乏三种倍半萜的释放，其中包括主要的倍半萜挥发物 (E)-β-石竹烯，这证实了先前对该基因的体外功能分配。基因 At5g44630 中携带 T-DNA 插入物的突变品系的花会释放出这三种倍半萜，但不会释放出任何其余的倍半萜挥发物。At5g44630 cDNA 在大肠杆菌中表达，产生的蛋白质催化二磷酸法尼酯转化为超过 15 种倍半萜，其比例与花香挥发混合物中的比例相似。At5g23960 和 At5g44630 启动子-β-葡萄糖醛酸酶（GUS）融合实验表明，这两个基因在拟南芥花的多个部位都有表达，其中 At5g23960 启动子-GUS 在柱头有很强的活性，而 At5g44630 则在花内蜜腺有很强的表达。鉴于之前报道的萜类化合物的抗菌活性，在柱头和蜜腺中产生萜类化合物可能有助于抑制这些脆弱部位的微生物感染。对 37 个拟南芥生态型的调查显示，花单萜烯和倍半萜烯的排放量存在数量上的差异，但几乎没有质量上的差异，这表明花萜烯挥发物在拟南芥植物的生命中一定扮演着重要角色。
• Surrogate Splicing for Functional Analysis of Sesquiterpene Synthase Genes
  作者：Shuiqin Wu、Mark A. Schoenbeck、Bryan T. Greenhagen、Shunji Takahashi、Sungbeom Lee、Robert M. Coates、Joseph Chappell

  DOI：10.1104/pp.105.059386

  日期：2005.7.1

  A method for the recovery of full-length cDNAs from predicted terpene synthase genes containing introns is described. The approach utilizes Agrobacterium-mediated transient expression coupled with a reverse transcription-polydeoxyribonucleotide chain reaction assay to facilitate expression cloning of processed transcripts. Subsequent expression of intronless cDNAs in a suitable prokaryotic host provides for direct functional testing of the encoded gene product. The method was optimized by examining the expression of an intron-containing β-glucuronidase gene agroinfiltrated into petunia (Petunia hybrida) leaves, and its utility was demonstrated by defining the function of two previously uncharacterized terpene synthases. A tobacco (Nicotiana tabacum) terpene synthase-like gene containing six predicted introns was characterized as having 5-epi-aristolochene synthase activity, while an Arabidopsis (Arabidopsis thaliana) gene previously annotated as a terpene synthase was shown to possess a novel sesquiterpene synthase activity for α-barbatene, thujopsene, and β-chamigrene biosynthesis.

  摘要：本文描述了一种从含有内含子的预测萜类合成酶基因中恢复全长cDNA的方法。该方法利用农杆菌介导的瞬时表达结合反转录-聚脱氧核苷酸链反应检测来促进已处理转录本的表达克隆。随后，在合适的原核宿主中表达无内含子的cDNA可直接进行编码基因产物的功能测试。通过研究农杆菌介导的内含子含有的β-葡萄糖醛酸酶基因在矮牵牛（Petunia hybrida）叶片中的表达来优化该方法，并通过确定两个先前未经表征的萜类合成酶的功能来证明其实用性。一个含有六个预测内含子的烟草（Nicotiana tabacum）萜类合成酶样基因被表征为具有5-epi-aristolochene合成酶活性，而一个先前注释为萜类合成酶的拟南芥（Arabidopsis thaliana）基因则显示出新颖的顺式-α-巴巴特烯、檀香烯和β-香茅烯生物合成的倍半萜合成酶活性。
• Enantioselective ring construction: synthesis of halogenated marine natural spiro[5.5]undecane sesquiterpenes
  作者：Julio D. Martin、Cirilo. Perez、Jose L. Ravelo

  DOI：10.1021/ja00284a052

  日期：1986.11

  (-)-33, and (8R,9R)-8-bromo-9-hydroxy-(E)-y-bisabolene, (+)-33, as the basic building blocks. This asymmetric methodology represents a general strategy for the enantioselective construction of spiro[5S]undecane systems containing a chiral quaternary center. This approach should be generally useful for the preparation of a wide variety of six-membered spirocycle-containing natural compounds. The compounds

  本研究的主要目标是开发一种通用方法，以在溴鎓引发的分子内碳环化反应中实现大量的不对称诱导。该目标已通过生成包含位于环己烯环上的两个立体原原子的环外亚烷基来实现。该过程的立体化学已经进行了一些详细的研究，并且全合成 (-)-(2R,6S,8S,9S)-2,8-dibromo-9-hydroxy-cr-chamigrene (9) , (- )-(2R,6S,8S,9S)-2,8-dibromo-9-hydroxy-fl-chamigrene (lo), (-)-(2R,6S)-2-bromo-fl-chamigrene (5), (-)-P-chamigrene (6) 及其相应的 (+)-11、-12、-7 和 -8 对映异构体首次被描述。这些化合物由 (8S,9S)-8-bromo-9-hydroxy-(E)-y-bisabolene、(-)-33 和 (8R,9R)-8-bromo-9