(-)-erythrodiene

• 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: (-)-erythrodiene
• 英文别名: (5S,7S)-4,10-dimethylidene-7-propan-2-ylspiro[4.5]decane
• 化学式: C₁₅H₂₄
• 分子量: 204.356
• InChiKey: WKUVNTPZIMJKBY-GJZGRUSLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  15
• 可旋转键数：
  1
• 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：

  (S)-(-)-紫苏醇 在 platinum(IV) oxide 、 四(三苯基膦)钯 正丁基锂 、 potassium tert-butylate 、 氢气 、 diethylzinc 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二甲基亚砜 、 苯 为溶剂， 反应 33.75h， 生成 (-)-erythrodiene
  参考文献：
  名称：

  烯丙基砜作为烯丙基锌在钯催化的锌-烯环化反应中的前体：对映纯（-）-红四烯的高效合成。

  摘要：

  易于制备的烯丙基苯基砜能够通过亲电α取代引入烯烃，优于乙酸烯丙酯作为Pd催化的Zn-烯环化的底物，提供具有顺式1,2-环的C5或C（4）N环。乙烯基和-CH（2）Zn取代基。提出了几种具有不同底物制备方法的实例。[反应：看文字]

  DOI：

  10.1021/ol051049i

文献信息

• Highly Diastereoselective Formation of Spirocyclic Compounds via 1,5-Hydrogen Transfer:  A Total Synthesis of (−)-Erythrodiene
  作者：Mathilde Lachia、Fabrice Dénès、Florent Beaufils、Philippe Renaud

  DOI：10.1021/ol051426r

  日期：2005.9.1

  A highly stereoselective synthesis of (-)-erythrodiene starting from 4-isopropylcyclohexanone is described. The key reactions are an asymmetric methoxycarbonylation of the starting ketone and a highly diastereoselective radical cascade involving addition of a phenylthiyl radical to a terminal alkyne followed by a 1,5-hydrogen transfer and a 5-exo-cyclization.
• Synthesis of (-)-erythrodiene via intramolecular Pd-catalyzed Zn-ene reaction
  作者：W. Oppolzer、F. Flachsmann

  DOI：10.1016/s0040-4039(98)00991-5

  日期：1998.7

  A highly diastereoselective synthesis of (-)-Erythrodiene was achieved via an intramolecular Pd-catalyzed Znene reaction as the key step. It was found that Pd(OAc)(2)/Bu3P was a superior catalyst for this reaction to Pd(PPh3)(4). (C) 1998 Elsevier Science Ltd. All rights reserved.
• Synthesis of (−)-Erythrodiene and (+)-7-Epispirojatamolvia Intramolecular Pd-Catalyzed Allylzincation
  作者：Wolfgang Oppolzer、Felix Flachsmann

  DOI：10.1002/1522-2675(20010228)84:2<416::aid-hlca416>3.0.co;2-k

  日期：2001.2.28

  Two spirobicyclic sesquiterpenoids, (-)-erythrodiene (1) and (+)-7-epispirojatamol (30),were synthesized in enantiomerically pure form via an intramolecular allylzincation process. The allylzinc species were formed in the presence of Et,Zn via transmetallation of a catalytically generated allylpalladium intermediate. Several Pd catalysts were tested for this transformation, and [Pd(OAc)(2)/Bu3P(1 equiv.) was found to be, by far, the most effective. Whereas the preparation of 1 involved allylzincation of a tethered terminal olefin. 30 was formed via a novel intramolecular allylzincation of a methyl ketone. Both reactions showed the same stereochemical preference. yielding the spirobicyclic products in 95:5 and 4:1 diastereoisomer ratios, respectively.
• Anti Selective Spirocarbomercuration: Synthesis and Stereochemistry of the Spirobicyclic Sesquiterpenes Spirojatamol and Erythrodiene
  作者：He Huang、Craig J. Forsyth

  DOI：10.1021/jo00114a027

  日期：1995.5

  The stereoselectivity of mercuric salt-induced spirocarbannulation reactions of substituted and unsubstituted 2-(4-pentynyl)-1-[(trimethylsilyl)oxy]cyclohexenes has been examined. This intramolecular alkyne carbomercuration reaction has been applied to the first enantioselective syntheses of the natural products erythrodiene and spirojatamol. Treatment of 2-(4-pentynyl)-1-[(trimethylsilyl)oxy]cyclohexene with HgCl2 gave 7(E)-mercuriomethylenespiro[4.5]decan-6-one, the product of anti selective carbomercuration. Similar intramolecular carbomercuration of (S)-4-isopropyl-2-(4-pentynyl)-1-[(trimethylsilyl)oxy]cyclohexene, derived from (S)-(-)-perillyl alcohol, gave diastereomeric axial and equatorial spirocarbannulation products in a 7:3 ratio and high yield. Both C-vinylation products, (1S and 1R,5S,7E)-5-isopropyl-7-mercuriomethylenespiro[5.4]decan-2-one), bear (E)-exocyclic vinyl mercurials. The major (1S,5S)-C-vinylation product was converted into both (-)-erythrodiene and (-)-spirojatamol in one and three steps, respectively. Thus, (-)-erythrodiene, a spirobicyclic sesquiterpene hydrocarbon from the Caribbean gorgonian coral Erythropodium caribaeorum, was synthesized from (S)-(-)-perillyl alcohol in 10 steps and approximately 35% overall yield using the mercuric salt-induced spirocarbannulation reaction as the key step. (-)-Spirojatamol, the enantiomer of the natural product isolated from the Indian plant Nardostachys jatamansi, was similarly prepared from (S)-(-)-perillyl alcohol in 12 steps and ca. 20% overall yield. This work indicates that the absolute configuration of (-)-erythrodiene ((1S,5S)-(-)-5-isopropyl-2,7-dimethylenespiro[5.4]decane) is enantiomeric to the carbon skeleton of (1S,5R,8S)-(+)-spirojatamol, the only other naturally occurring sesquiterpene known to posses the 5-isopropyl-2-methylenespiro[5.4]decane skeleton.
• Allyl Sulfones as Precursors to Allylzincs in the Palladium-Catalyzed Zinc-ene Cyclization:  Highly Efficient Synthesis of Enantiopure (−)-Erythrodiene
  作者：Kai Deng、Justin Chalker、Ao Yang、Theodore Cohen

  DOI：10.1021/ol051049i

  日期：2005.8.1

  Easily prepared allyl phenyl sulfones, capable of introduction of the alkene by electrophilic alpha-substitution, are superior to allyl acetates as substrates for Pd-catalyzed Zn-ene cyclizations, providing C5 or C(4)N rings with cis-1,2-vinyl and -CH(2)Zn substituents. Several examples, with different methods of substrate preparation, are presented. [reaction: see text]

  易于制备的烯丙基苯基砜能够通过亲电α取代引入烯烃，优于乙酸烯丙酯作为Pd催化的Zn-烯环化的底物，提供具有顺式1,2-环的C5或C（4）N环。乙烯基和-CH（2）Zn取代基。提出了几种具有不同底物制备方法的实例。[反应：看文字]