4,4,8a-trimethyl-Δ⁸-carbomethoxy-trans-octahydronaphthalene | 132982-84-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 4,4,8a-trimethyl-Δ⁸-carbomethoxy-trans-octahydronaphthalene
• 英文别名: 1-carbomethoxy-5,5,8a-trimethyl-trans-3,4,4a,5,6,7,8,8a-octahydronaphthalene；(+/-)-5,5,8a-trimethyl-(4ar,8at)-3,4,4a,5,6,7,8,8a-octahydro-[1]naphthoic acid methyl ester；(+/-)-5,5,8a-Trimethyl-(4ar,8at)-3,4,4a,5,6,7,8,8a-octahydro-[1]naphthoesaeure-methylester；methyl (4aS,8aS)-5,5,8a-trimethyl-3,4,4a,6,7,8-hexahydronaphthalene-1-carboxylate
• CAS: 132982-84-4
• 化学式: C₁₅H₂₄O₂
• 分子量: 236.354
• InChiKey: TTWWFQKTTFXNEY-SWLSCSKDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,4,8a-trimethyl-Δ⁸-carbomethoxy-trans-octahydronaphthalene 在 palladium on activated charcoal 3,5-二甲基吡唑 、 chromium(VI) oxide 、 sodium tetrahydroborate 、 氢气 、 lithium carbonate 、 sodium hydride 、 lithium bromide 作用下， 以 吡啶 、 乙二醇二甲醚 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 42.5h， 生成 dimethyl (4aRS,5SR,8aRS)-1,2,3,4,4a,5,8,8a-octahydro-1,1,4a-trimethylnaphthalene-5,6-dicarboxylate
  参考文献：
  名称：

  An alternative Route to (±)-Warburganal Synthon

  摘要：

  The transformation of the ketone (1) to the unsaturated diester (11) a potential intermediate for the warburganal (12) is described. The Wittig reaction of theketone (1) with methylenelriphenylphosphorane afforded the olefin (2) which reacts with Woodward's reagent (MeCOOAg, I-2 and MeCOOH and H2O) to give the diol (13). This on heating with dimethylsulfoxide afforded the tetralin (14).

  DOI：

  10.1080/00397910008087060
• 作为产物：
  描述：

  (+-)-5,5,8a-trimethyl-(4ar,8at)-octahydro-naphthalen-1-one 在 4-二甲氨基吡啶 、 sodium hydroxide 、 selenium(IV) oxide 、 N-甲基吲哚酮 、 四丙基高钌酸铵 、 sodium amide 、 N,N'-二环己基碳二亚胺 作用下， 以 乙醇 、 二氯甲烷 、 溶剂黄146 、 甲苯 为溶剂， 反应 19.0h， 生成 4,4,8a-trimethyl-Δ⁸-carbomethoxy-trans-octahydronaphthalene
  参考文献：
  名称：

  An alternative Route to (±)-Warburganal Synthon

  摘要：

  The transformation of the ketone (1) to the unsaturated diester (11) a potential intermediate for the warburganal (12) is described. The Wittig reaction of theketone (1) with methylenelriphenylphosphorane afforded the olefin (2) which reacts with Woodward's reagent (MeCOOAg, I-2 and MeCOOH and H2O) to give the diol (13). This on heating with dimethylsulfoxide afforded the tetralin (14).

  DOI：

  10.1080/00397910008087060

文献信息

• Untersuchungen über den sterischen Verlauf säure-katalysierter Cyclisationen bei terpenoiden Polyenverbindungen. 1. Mitteilung. Cyclisation der 7,11-Dimethyl-2(trans), 6(trans), 10-dodecatrien-und der 7, 11-Dimethyl-2(cis), 6(trans), 10-dodecatrien-säure
  作者：P. A. Stadler、A. Nechvatal、A. J. Frey、A. Eschenmoser.

  DOI：10.1002/hlca.19570400527

  日期：——

  stereoisomeren Triensäuren bzw. deren Methylester dargestellt und der Verlauf ihrer säure-katalysierten Cyclisation untersucht. Im System Ameisensäure- Schwefelsäure verliefen die Ringschlussreaktionen sowohl in struktureller als auch in sterischer Hinsicht weitgehend selektiv und führten zu den auf Grund des trans-Additionsschemas zu erwartenden Derivaten des trans-Decalins.

  介绍了标题中提及的立体异构体三烯酸或其甲酯，并研究了其酸催化的环化过程。在甲酸-硫酸体系中，闭环反应在结构和空间上都具有很大的选择性，并导致在反式加成方案的基础上可以预期反式十氢化萘的衍生物。
• New radical reactions of S-alkoxycarbonyl xanthates. Total synthesis of (±)-cinnamolide and (±)-methylenolactocin
  作者：Judith E Forbes、Radomir N Saicic、Samir Z Zard

  DOI：10.1016/s0040-4020(98)01184-3

  日期：1999.3

  with visible light of S-alkoxycarbonyl xanthates derived from various alcohols gives rise to alkoxycarbonyl radicals with bifurcate reactivity: loss of carbon dioxide leads to deoxygenated derivatives (i.e. alkyl xanthates) whereas intramolecular addition to a suitably located double bond produces lactones; these new reactions were applied to the total synthesis of (±)-cinnamolide and (±)-methylenolactocin

  用可见光照射衍生自各种醇的S-烷氧羰基黄药生成具有分叉反应性的烷氧羰基基团：二氧化碳的损失导致脱氧衍生物（即烷基黄药），而分子内加成至适当位置的双键则产生内酯；这些新的反应被应用于（±）-肉桂酸酯和（±）-甲基烯醇内酯的全合成。
• Aromatic Annulation Strategy for the Synthesis of Angularly-Fused Diterpenoid Quinones. Total Synthesis of (+)-Neocryptotanshinone, (-)-Cryptotanshinone, Tanshinone IIA, and (.+-.)-Royleanone
  作者：Rick L. Danheiser、David S. Casebier、Fariborz Firooznia

  DOI：10.1021/jo00131a006

  日期：1995.12

  The application of a photochemical aromatic annulation strategy in highly efficient total syntheses of several diterpenoid quinones isolated from the traditional Chinese medicine Dan Shen is reported. The pivotal step in each synthesis involves the assembly of a key tricyclic intermediate via the application of a recently developed ''second-generation'' photochemical aromatic annulation method for the construction of highly substituted aromatic systems. In the total synthesis of neocrypto-tanshinone,;the synthesis of the requisite diazo ketone annulation substrate 7 was achieved using palladium-mediated coupling reactions and an intramolecular Friedel-Crafts cyclization to form key carbon-carbon bonds. The pivotal aromatic annulation reaction was then accomplished by irradiating a solution of the diazo ketone 7 and the readily available siloxyalkyne 6 in benzene at room temperature. The desired tricyclic phenol 16 was produced in 58-65% yield and was then converted to (+)-neocryptotanshinone (1) by treatment with tetra-n-butylammonium fluoride in the presence of oxygen. Cyclization to generate (-)-cryptotanshinone (2) was accomplished in high yield by brief exposure of 1 to an ethanolic solution of concentrated sulfuric acid, and dehydrogenation of 2 with DDQ furnished tanshinone IIA (3). As a further demonstration of the utility of the photochemical aromatic annulation strategy in the construction of angularly-fused diterpenes, the total synthesis of(+/-)-royleanone (4) was also investigated. Irradiation of a solution of the diazo ketone 18 and siloxyalkyne 25 produced the tricyclic intermediate 26, which was converted in two steps to royleanone by desilylation and oxidation.
• An alternative Route to (±)-Warburganal Synthon
  作者：Ajoy K. Banerjee、Viviane E. Khalil、William Vera

  DOI：10.1080/00397910008087060

  日期：2000.12

  The transformation of the ketone (1) to the unsaturated diester (11) a potential intermediate for the warburganal (12) is described. The Wittig reaction of theketone (1) with methylenelriphenylphosphorane afforded the olefin (2) which reacts with Woodward's reagent (MeCOOAg, I-2 and MeCOOH and H2O) to give the diol (13). This on heating with dimethylsulfoxide afforded the tetralin (14).