(+)-γ-polypodatetraene | 88902-03-8

• 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: (+)-γ-polypodatetraene
• 英文别名: γ-polypodatetraene；(4aS,8S,8aS)-4,4,7,8a-tetramethyl-8-[(3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienyl]-1,2,3,4a,5,8-hexahydronaphthalene
• CAS: 88902-03-8
• 化学式: C₃₀H₅₀
• 分子量: 410.727
• InChiKey: HPKNCAAZGBOERA-XXPUDMTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.8
• 重原子数：
  30
• 可旋转键数：
  9
• 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：

  角鲨烯 在 squalene-hopene cyclase Leu₆₀₇Lys mutant 作用下， 生成 (+)-γ-polypodatetraene
  参考文献：
  名称：

  Specific production of γ-polypodatetraene or 17-isodammara-20(21),24-diene by squalene–hopene cyclase mutant

  摘要：

  Amino acids lining the catalytic cavity of squalene-hopene cyclase of Alicyclobacillus acidocaldarius were mutated to investigate their catalytic functions. Mutagenesis of Leu607 to Lys in the central part of the cavity resulted in the production of the bicyclic gamma -polypodatetraene (1) as main product, while the mutation of Phe605 to Lys near the deprotonation site of the cavity led mainly to the formation of tetracyclic 17-isodammara-20(21),24-diene (2). (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)02149-3

文献信息

• First Synthesis of (+)-.ALPHA.-and (+)-.GAMMA.-Polypodatetraenes.
  作者：Masako Kinoshita、Mahisa Ohtsuka、Daisuke Nakamura、Hiroyuki Akita

  DOI：10.1248/cpb.50.930

  日期：——

  First synthesis of (+)-α-polypodatetraene (1) and (+)-γ-polypodatetraene (2) was achieved from (+)-albicanol (6) and (−)-drimenol (8), respectively. The absolute structure of natural (+)-2 was established to be (5S,9S,10S)-polypoda-7,13(E),17(E),21-tetraene.

  分别从(+)-albicanol (6)和(-)-drimenol (8)首次合成了(+)-α-聚十二碳四烯(1)和(+)-γ-聚十二碳四烯(2)。天然(+)-2的绝对结构被确定为(5S,9S,10S)-聚-7,13(E),17(E),21-四烯。
• <i>Alicyclobacillus acidocaldarius</i> Squalene‐Hopene Cyclase: The Critical Role of Steric Bulk at Ala306 and the First Enzymatic Synthesis of Epoxydammarane from 2,3‐Oxidosqualene
  作者：Natsumi Ideno、Shikou Umeyama、Takashi Watanabe、Mami Nakajima、Tsutomu Sato、Tsutomu Hoshino

  DOI：10.1002/cbic.201800281

  日期：2018.9.4

  SHC is widely conserved in known SHCs. Increases in steric bulk (A306T and A306V) led to the accumulation of 6,6,6,5‐fused tetracyclic scaffolds with 20R stereochemistry. This indicates folding of squalene in a chair‐chair‐chair‐boat conformation. The stereochemical fate in polycyclization is thus governed by the bulk at this position.

  Polycyclization和构象分析：Ala306在A.热硫化叶菌SHC广泛保守已知的特困家庭。空间体积（A306T和A306V）的增加导致具有20 R立体化学的6,6,6,5融合的四环支架的积累。这表明角鲨烯折叠成椅子-椅子-船构型。因此，多环化中的立体化学命运受该位置的主体支配。
• Functional Analyses of Tyr420 and Leu607 of <i>Alicyclobacillus acidocaldarius</i> Squalene-Hopene Cyclase. Neoachillapentaene, a Novel Triterpene with the 1,5,6-Trimethylcyclohexene Moiety…
  作者：Tsutomu SATO、Shigehiro SASAHARA、Toshiyuki YAMAKAMI、Tsutomu HOSHINO

  DOI：10.1271/bbb.66.1660

  日期：2002.1.1

  The functions of Tyr420 and Leu607 were analyzed by constructing various site-directed mutants. The mutation at position 420 into Ala and Gly gave bicyclic α- and γ-polypodatetraene in significant amounts, but with a trace amount of tricyclic malabaricatriene. The kinetic data for and the product distribution of the Y420F mutant indicate that the major function of Tyr420 is to stabilize the 6/6-fused bicyclic cation. Mutation experiments on Leu607 demonstrate that the appropriate steric bulk size at position 607 is required to strongly bind with the product-like conformation formed during the polycyclization process. Introduction of the bulkiest Trp residue into 420 or 607 led to the production of a novel monocyclic triterpene having the (5R,6R)-1,5,6-trimethylcyclohexene ring, named neoachillapentaene, indicating that the enzymatic cyclization proceeded via a constrained boat structure. Folding of the squalene molecule into a boat conformation by squalene cyclase has not been reported before.

  通过构建各种定点突变体，分析了 Tyr420 和 Leu607 的功能。将 420 位突变为 Ala 和 Gly 会产生大量的双环 α- 和 γ-聚十二碳四烯，但会产生微量的三环马拉巴里三烯。Y420F 突变体的动力学数据和产物分布表明，Tyr420 的主要功能是稳定 6/6 融合双环阳离子。对 Leu607 的突变实验表明，在多环化过程中形成的类似产物构象需要在 607 位有适当的立体体积才能与之紧密结合。将体积最大的 Trp 残基引入 420 位或 607 位后，产生了一种具有 (5R,6R)-1,5,6-三甲基环己烯环的新型单环三萜，命名为新水苏烯，这表明酶促环化是通过受限的舟状结构进行的。角鲨烯分子通过角鲨烯环化酶折叠成舟形构象的情况以前从未报道过。
• Catalytic Function of the Residues of Phenylalanine and Tyrosine Conserved in Squalene-Hopene Cyclases
  作者：Tsutomu SATO、Tsutomu HOSHINO

  DOI：10.1271/bbb.65.2233

  日期：2001.1

  trapping of the prematurely cyclized products: (1) The Y495 residue probably amplifies the D376 acidity, which is assumed to work as a proton donor for initiating the polycyclization cascade, but its role is moderate. (2) Y609 possibly assists the function of F365, which has previously been assigned to exclusively stabilize the C-8 carbocation intermediate through cation-pi interaction. The Y609A mutant produced

  在所有已知的角鲨烯-戊二烯环化酶（SHC）中对Phe和Tyr的所有保守残基进行了定点诱变实验，以鉴定嗜酸酸热脂环芽孢杆菌SHC的活性位点残基。根据动力学数据和过早环化产物的捕集，提出了以下功能：（1）Y495残基可能会放大D376的酸度，假定该酸可作为质子供体启动多环化级联反应，但其作用是中等。（2）Y609可能有助于F365的功能，F365先前已被指定通过阳离子-π相互作用专门稳定C-8碳阳离子中间体。Y609A突变体产生了部分环化的双环三萜。（3）Y612可稳定C10和C8碳正离子，通过发现与Y612A突变体形成单环和双环产物，证实了这一点。（4）F129首先被确定在催化中起关键作用。（5）三个残基Y372，Y474和Y540负责增强蛋白质结构抵抗热变性，Y474位于QW基序3的内部。
• Selective total synthesis of (±)-α- and γ-polypodatetraene
  作者：Mugio Nishizawa、Hisaya Nishide、Yuji Hayashi

  DOI：10.1039/c39840000467

  日期：——

  The fern metabolites, α-and γ-polypodatetraene, possible biosynthetic intermediates of onocerane type triterpenoids, are selectively synthesized by mercury(II) trifluoromethanesulphonate–amine complex-induced olefin cyclization followed by simple chemical transformations.

  蕨类代谢物，α-和γ-聚戊四烯，可能是胭脂烷型三萜类化合物的生物合成中间体，是由汞（II）三氟甲磺酸-胺络合物诱导的烯烃环化选择性地合成的，然后进行简单的化学转化。