(+)-α-polypodatetraene

• 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: (+)-α-polypodatetraene
• 英文别名: (4aS,8S,8aS)-4,4,8a-trimethyl-7-methylidene-8-[(3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienyl]-2,3,4a,5,6,8-hexahydro-1H-naphthalene
• 化学式: C₃₀H₅₀
• 分子量: 410.727
• InChiKey: IPRRCLUFQNXFGA-XXPUDMTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11
• 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：

  ((1S,8aS)-5,5,8a-trimethyl-2-methylene-decahydronaphthalen-1-yl)methyl methanesulfonate 在 甲醇 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 sodium amalgam 、 四溴化碳 、 二异丁基氢化铝 、 对甲苯磺酰氯 、 三苯基膦 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 甲苯 、 苯 为溶剂， 反应 50.0h， 生成 (+)-α-polypodatetraene
  参考文献：
  名称：

  First Synthesis of (+)-.ALPHA.-and (+)-.GAMMA.-Polypodatetraenes.

  摘要：

  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。

  DOI：

  10.1248/cpb.50.930

文献信息

• Chemoenzymatic Synthesis of (+)-.ALPHA.-Polypodatetraene and Methyl (5R,10R,13R)-Labda-8-en-15-oate
  作者：Masako Kinoshita、Takahiro Miyake、Yuusuke Arima、Minako Oguma、Hiroyuki Akita

  DOI：10.1248/cpb.56.118

  日期：——

  The reported enzymatic resolution products acetate of (1S,4aS,8aS)-1,2,3,4,4a,5,6,7,8,8a-decahydro-5,5,8a-trimethyl-2-oxo-trans-naphthalene-1-methanol-2-ethylene acetal} (8aS)-5 (>99% ee)] and [(1R,4aR,8aR)-1,2,3,4,4a,5,6,7,8,8a-decahydro-5,5,8a-trimethyl-2-oxo-trans-naphthalene-1-methanol-2-ethylene acetal (8aR)-4 (98% ee) were converted to (+)-α-polypodatetraene (1) and methyl (5R,10R,13R)-labda-8-en-15-oate (2), respectively. For the synthesis of (5R,10R,13R)-2, chiral isoprene congener (3S)-26 corresponding to the right part of 2 was synthesized based on the lipase-assisted resolution of (±)-2-methyl-3- (p-methoxyphenyl)propanol (17).

  已报道的酶解产物(1S,4aS,8aS)-1,2,3,4,4a,5,6,7,8,8a-十氢-5,5,8a-三甲基-2-氧代-反式-萘-1-甲醇-2-乙烯缩醛的乙酸酯} (8aS)-5 (>99% ee)]和[(1R,4aR,8aR)-1,2,3,4、4a,5,6,7,8,8a-十氢-5,5,8a-三甲基-2-氧代-反式-萘-1-甲醇-2-乙烯缩醛 (8aR)-4 (98% ee)]分别转化为 (+)-α-polypodatetraene (1) 和 (5R,10R,13R)-labda-8-烯-15-酸甲酯 (2)。为了合成 (5R,10R,13R)-2，根据脂肪酶辅助解析 (±)-2- 甲基-3-（对甲氧基苯基）丙醇 (17) 的方法，合成了对应于 2 右半部分的手性异戊二烯同系物 (3S)-26。
• <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。
• 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。
• Production of bicyclic and tricyclic triterpenes by mutated squalene-hopene cyclase
  作者：Catherine Pale-Grosdemange、Thorsten Merkofer、Michel Rohmer、Karl Poralla

  DOI：10.1016/s0040-4039(99)01248-4

  日期：1999.8

  Mutagenesis of Tyr420 to Ala in the catalytic cavity of squalene-hopene cyclase of Alicyclobacillus acidocaldarius resulted in an altered product spectrum. Besides hopene and diplopterol, this mutant produced significant amounts of the bicyclic alpha- and gamma-polypodatetraenes and minor amounts of the tricyclic 13 alpha(H)-malabaricatriene. (C) 1999 Published by Elsevier Science Ltd. All rights reserved.