methyl (4aR,8aR)-2-diethoxyphosphoryloxy-5,5,8a-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalene-1-carboxylate | 534600-61-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 英文名称: methyl (4aR,8aR)-2-diethoxyphosphoryloxy-5,5,8a-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalene-1-carboxylate
• 英文别名: methyl (4aR,8aR)-2-diethoxyphosphoryloxy-5,5,8a-trimethyl-3,4,4a,6,7,8-hexahydronaphthalene-1-carboxylate
• CAS: 534600-61-8
• 化学式: C₁₉H₃₃O₆P
• 分子量: 388.441
• InChiKey: POLFXVXCAZWQBF-DNVCBOLYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl (4aR,8aR)-2-diethoxyphosphoryloxy-5,5,8a-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalene-1-carboxylate 在 吡啶 、 sodium hydroxide 、 copper(l) iodide 、 potassium tert-butylate 、 三溴化磷 、 二异丁基氢化铝 作用下， 以 乙醚 、 二甲基亚砜 、 甲苯 为溶剂， 反应 20.17h， 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：

  methyl (1S,4aS,8aR)-2,2-ethylenedioxy-5,5,8a-trimethyl-1,2,3,4,4a,5,8,8a-octahydronapthalene-1-carboxylate 在 palladium on activated charcoal 盐酸 、 氢气 、 sodium hydride 作用下， 以 四氢呋喃 、 乙酸乙酯 为溶剂， 反应 46.0h， 生成 methyl (4aR,8aR)-2-diethoxyphosphoryloxy-5,5,8a-trimethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalene-1-carboxylate
  参考文献：
  名称：

  (-)-辛二酸的合成和绝对构型，一种海绵衍生的人 15-脂氧合酶的萜类抑制剂

  摘要：

  (-)-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)

  DOI：

  10.1002/ejoc.200390128

文献信息

• The inhibitory mechanism of bovine pancreatic phospholipase A2 by aldehyde terpenoids
  作者：Katsunori Tanaka、Mitsunobu Kamatani、Hajime Mori、Shinobu Fujii、Kiyoshi Ikeda、Miki Hisada、Yasuhiro Itagaki、Shigeo Katsumura

  DOI：10.1016/s0040-4020(98)01197-1

  日期：1999.2

  We established the stereoselective synthesis of (E)-3-methoxycarbonyl-2,4,6-trienal compound A and discovered that the compound A showed more powerful inhibitory activity toward phospholipase A2(PLA2) from bovine pancreas than manoalide which is a typical PLA2 inhibitor. As the inhibitory mechanism of PLA2 by A, the irreversible formation of dihydropyridine derivative resulting from the reaction of

  我们建立了（E）-3-甲氧基羰基-2,4,6-三烯醛化合物A的立体选择性合成方法，发现该化合物A对牛胰腺中磷脂酶A 2（PLA 2）的抑制作用比对作为主体的Manoalide具有更强的抑制作用。典型的PLA 2抑制剂。作为PLA的抑制机构2由甲，二氢吡啶衍生物由此而来从反应不可逆地形成甲与PLA赖氨酸残基2是基于模型的反应方案。此外，A 通过MALDI-TOF-MS肽图分析发现，Lys56被选择性地修饰了包括在该酶的界面识别位点中的Lys56。
• First synthesis of (−)-spongianolide A and determination of its absolute structure
  作者：Toshiyuki Hata、Katsunori Tanaka、Shigeo Katsumura

  DOI：10.1016/s0040-4039(99)00039-8

  日期：1999.2

  The first synthesis of (−)-spongianolide A (1), a cytotoxic sesterterpenoid, and determination of its absolute structure are described. In this synthesis, a simple and practical method for preparation of enantiomerically pure bicyclic and tricyclic β-ketoesters, and a new Wittig reagent, furanmethylide, were developed.

  描述了（-）-海绵状内酯A（1）的首次合成，细胞毒性的酯类萜类化合物及其绝对结构的确定。在该合成中，开发了一种简单，实用的对映体纯的双环和三环β-酮酸酯的制备方法，并开发了一种新的Wittig试剂呋喃甲基化物。
• Mori, Kenji; Koga, Yasuo, Liebigs Annalen der Chemie, 1991, # 8, p. 769 - 774
  作者：Mori, Kenji、Koga, Yasuo

  DOI：——

  日期：——
• 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)
• 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.