(5R,10R,13E)-8(9),13-labdadien-15-ol | 61217-44-5

• 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: (5R,10R,13E)-8(9),13-labdadien-15-ol
• 英文别名: ent-Labda-8,E-13-dien-15-ol；(E)-5-[(4aR,8aR)-2,5,5,8a-tetramethyl-3,4,4a,6,7,8-hexahydronaphthalen-1-yl]-3-methylpent-2-en-1-ol
• CAS: 61217-44-5
• 化学式: C₂₀H₃₄O
• 分子量: 290.489
• InChiKey: IOHVFDUBRDGOCE-JAGYYFLNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (5R,10R,13E)-8(9),13-labdadien-15-ol 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 吡啶 、 lithium chloride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 7.0h， 生成
  参考文献：
  名称：

  Natural product synthesis from (8aR)- and (8aS)-bicyclofarnesols: synthesis of (+)-wiedendiol A, (+)-norsesterterpene diene ester and (−)-subersic acid

  摘要：

  Both enantiomers (8aR)-7 and (8aS)-7 of bicyclofarnesol were synthesized from the enzymatic resolution products (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)-5 (98% ee) and 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)-6 (> 99% ee), respectively. The formal synthesis of (+)-wiedendiol 1 was achieved via a coupling reaction of an ate complex derived from 1,2,4-trimethoxybenzene with allyl bromide (8aS)-8 derived from (8aS)-7. The total synthesis of (+)-norsesterterpene diene ester 2 was achieved, based on the synthesis of (13E,10S)-alpha,beta-unsaturated aldehyde 12, derived from (8aS)-7, followed by the selective construction of the (3E,5E)-diene moiety including a C(2)-stereogenic centre in (+)-2. The total synthesis of (-)-subersic acid 3 was carried out based on a Stille coupling between allyl trifluoroacetate congener 25c, derived from (8aR)-7, corresponding to the diterpene part, and aryl stannane congener 26 in the presence of Pd catalyst and CuI as an additive. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2007.07.010
• 作为产物：
  描述：

  methyl (4aS*,8aS*)-3,4,4a,5,6,7,8,8a-octahydro-2,5,5,8a-tetramethylnaphthalene-1-carboxylate 在 吡啶 、 sodium hydroxide 、 potassium tert-butylate 、 三溴化磷 、 sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二甲基亚砜 、 甲苯 为溶剂， 反应 33.34h， 生成 (5R,10R,13E)-8(9),13-labdadien-15-ol
  参考文献：
  名称：

  Natural product synthesis from (8aR)- and (8aS)-bicyclofarnesols: synthesis of (+)-wiedendiol A, (+)-norsesterterpene diene ester and (−)-subersic acid

  摘要：

  Both enantiomers (8aR)-7 and (8aS)-7 of bicyclofarnesol were synthesized from the enzymatic resolution products (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)-5 (98% ee) and 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)-6 (> 99% ee), respectively. The formal synthesis of (+)-wiedendiol 1 was achieved via a coupling reaction of an ate complex derived from 1,2,4-trimethoxybenzene with allyl bromide (8aS)-8 derived from (8aS)-7. The total synthesis of (+)-norsesterterpene diene ester 2 was achieved, based on the synthesis of (13E,10S)-alpha,beta-unsaturated aldehyde 12, derived from (8aS)-7, followed by the selective construction of the (3E,5E)-diene moiety including a C(2)-stereogenic centre in (+)-2. The total synthesis of (-)-subersic acid 3 was carried out based on a Stille coupling between allyl trifluoroacetate congener 25c, derived from (8aR)-7, corresponding to the diterpene part, and aryl stannane congener 26 in the presence of Pd catalyst and CuI as an additive. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2007.07.010

文献信息

• Studies in terpenoid biosynthesis. Part IV. Biosynthesis of the kaurenolides and gibberellic acid
  作者：J. R. Hanson、A. F. White

  DOI：10.1039/j39690000981

  日期：——

  the kaurenolides, and gibberellic acid. The labelling pattern from 4-(R)-[4-3H]- and 2-[3H2]-mevalonic acid in these tetracyclic diterpenes has been determined and this evidence is used to exclude (–)-primara-7,8- and -8,9-dienes from the biosynthesis. (–)Pimara-8(14)-diene has been shown to be specifically incorporated into the kaurenolides and gibberellic acid. The stereochemistry of hydroxylation

  香叶基香叶醇和（–）-labda-8,13-dien-15-ol焦磷酸盐已被证明可作为（–）-贝壳杉烯，金脲内酯和赤霉素的前体。4-（R）-[4- 3 H]-和2- [ 3 H 2这些四环二萜中的]-甲羟戊酸已被测定，该证据用于从生物合成中排除（-）-primara-7,8-和-8,9-二烯。已证明（–）Pimara-8（14）-二烯特别掺入了金脲内酯和赤霉素中。赤霉素A环的羟基化的立体化学已经显示出保持构型。在C-19赤霉素的形成中失去角C-20原子不涉及4-，4b-或10a-不饱和酸的脱羧。
• MERCURY(II) TRIFLATE—AMINE COMPLEX-INDUCED CYCLIZATION OF GERANYLGERANYL<i>p</i>-NITROBENZOATE: SYNTHESIS OF SPONDIAN AND LABDANE DITERPENOIDS
  作者：Mugio Nishizawa、Hideyuki Takenaka、Yuji Hayashi

  DOI：10.1246/cl.1983.1459

  日期：1983.9.5

  Biomimetic cyclization of geranylgeranyl p-nitrobenzoate by the mercury(II) triflate—N,N-dimethylaniline complex and subsequent reductive demercuration provide a tricyclic and two bicyclic diterpenoids in moderate yields. This is the first example of the cyclization of geranylgeraniol to the tricyclic diterpene.

  通过三late-N,N-二甲基苯胺汞(II)络合物对对硝基苯甲酸香叶酯的生物模拟环化以及随后的还原脱氢反应，以中等产率获得了一种三环和两种双环二萜化合物。这是第一个将香叶基苯二酚环化成三环二萜的例子。
• Neutral diterpenes from Araucaria bidwilli
  作者：Romualdo Caputo、Lorenzo Mangoni、Pietro Monaco、Laura Pelosi、Lucio Previtera

  DOI：10.1016/s0031-9422(00)97126-7

  日期：1976.1
• Chemical simulation of polycyclic diterpenoid biosynthesis using mercury(II) triflate/N,N-dimethylaniline complex: mechanistic aspects of a biomimetic olefin cyclization
  作者：Mugio Nishizawa、Hideyuki Takenaka、Yuji Hayashi

  DOI：10.1021/jo00356a008

  日期：1986.3
• Natural product synthesis from (8aR)- and (8aS)-bicyclofarnesols: synthesis of (+)-wiedendiol A, (+)-norsesterterpene diene ester and (−)-subersic acid
  作者：Yuusuke Arima、Masako Kinoshita、Hiroyuki Akita

  DOI：10.1016/j.tetasy.2007.07.010

  日期：2007.7

  Both enantiomers (8aR)-7 and (8aS)-7 of bicyclofarnesol were synthesized from the enzymatic resolution products (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)-5 (98% ee) and 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)-6 (> 99% ee), respectively. The formal synthesis of (+)-wiedendiol 1 was achieved via a coupling reaction of an ate complex derived from 1,2,4-trimethoxybenzene with allyl bromide (8aS)-8 derived from (8aS)-7. The total synthesis of (+)-norsesterterpene diene ester 2 was achieved, based on the synthesis of (13E,10S)-alpha,beta-unsaturated aldehyde 12, derived from (8aS)-7, followed by the selective construction of the (3E,5E)-diene moiety including a C(2)-stereogenic centre in (+)-2. The total synthesis of (-)-subersic acid 3 was carried out based on a Stille coupling between allyl trifluoroacetate congener 25c, derived from (8aR)-7, corresponding to the diterpene part, and aryl stannane congener 26 in the presence of Pd catalyst and CuI as an additive. (c) 2007 Elsevier Ltd. All rights reserved.