(-)-[(4aR,8aR)-2,5,5,8a-tetramethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-1-yl]methanol | 534600-63-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-[(4aR,8aR)-2,5,5,8a-tetramethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-1-yl]methanol
• 英文别名: [(4aR,8aR)-2,5,5,8a-tetramethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-1-yl]methanol；β-bicyclofarnesol；(8aR)-bicyclofarnesol；(8aR)-cyclofarnesol；[(4aR,8aR)-2,5,5,8a-tetramethyl-3,4,4a,6,7,8-hexahydronaphthalen-1-yl]methanol
• CAS: 534600-63-0
• 化学式: C₁₅H₂₆O
• 分子量: 222.371
• InChiKey: HEFHXIIJACYLNN-HIFRSBDPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.87
• 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：

  (-)-[(4aR,8aR)-2,5,5,8a-tetramethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-1-yl]methanol 在 吡啶 、 sodium hydroxide 、 potassium tert-butylate 、 三溴化磷 作用下， 以 乙醚 、 二甲基亚砜 为溶剂， 反应 15.17h， 生成 5β,10α-14,15,Dinor-8-labden-13-on
  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：

  (7E)-9-ethynyl-β-ionol 在 palladium on activated charcoal potassium sulfate 、 potassium hydrogensulfate 、 lithium aluminium tetrahydride 、 oxone 、 韦德伊斯试剂 、 氢气 、 三乙胺 、 2-萘乙酮 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 四氯化碳 、 乙醚 、 乙醇 、 二氯甲烷 、 水 、 苯 为溶剂， 反应 16.0h， 生成 (-)-[(4aR,8aR)-2,5,5,8a-tetramethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-1-yl]methanol
  参考文献：
  名称：

  Allenyldiene electrocyclization, a stereospecific tandem center-axis-center chirality transfer: synthesis of drimatrienes and related trans-decalins

  摘要：

  DOI：

  10.1021/ja00290a047

文献信息

• Synthesis and Absolute Configuration of (−)-Subersic Acid, a Sponge-Derived, Terpenoidal Inhibitor of Human 15-Lipoxygenase
  作者：Yoshihisa Tanada、Kenji Mori

  DOI：10.1002/ejoc.200390128

  日期：2003.3

  (−)-Subersic acid (1), a new derivative of p-hydroxybenzoic acid in which the m-position is substituted with a bicyclic diterpenoid, was synthesized from (S)-3-hydroxy-2,2-dimethylcyclohexanone and p-hydroxybenzoic acid. The stereochemistry of this sponge-derived inhibitor of human 15-lipoxygenase was established as (5R,10R)-1. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

  (-)-辛二酸 (1) 是一种对羟基苯甲酸的新衍生物，其中间位被双环二萜类化合物取代，由 (S)-3-羟基-2,2-二甲基环己酮和对-羟基苯甲酸。这种海绵衍生的人 15-脂肪氧化酶抑制剂的立体化学被确定为 (5R,10R)-1。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• 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。
• Allenyldiene electrocyclization, a stereospecific tandem center-axis-center chirality transfer: synthesis of drimatrienes and related trans-decalins
  作者：William H. Okamura、Roland Peter、Wolfgang Reischl

  DOI：10.1021/ja00290a047

  日期：1985.2
• 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.