4a-methyl-2,5-dioxo-2,3,4,4a,5,6,7,8-octahydro-[1]naphthoic acid ethyl ester | 3733-18-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4a-methyl-2,5-dioxo-2,3,4,4a,5,6,7,8-octahydro-[1]naphthoic acid ethyl ester
• 英文别名: 4a-Methyl-2,5-dioxo-2,3,4,4a,5,6,7,8-octahydro-[1]naphthoesaeure-aethylester；10-Methyl-1-ethoxycarbonyl-Δ¹⁽⁹⁾-octalindion-(2,5)；4-Carbethoxy-9-methyl-Δ^4,10-octalin-3,8-dion；2,5-Dioxo-4a-methyl-2,3,4,4a,5,6,7,8-octahydronaphthalene-1-carboxylic acid ethyl ester；ethyl 4a-methyl-2,5-dioxo-4,6,7,8-tetrahydro-3H-naphthalene-1-carboxylate
• CAS: 3733-18-4
• 化学式: C₁₄H₁₈O₄
• 分子量: 250.295
• InChiKey: JJBCOYHHOYPMGC-UHFFFAOYSA-N

物化性质

• 熔点：
  76-78 °C
• 沸点：
  174-177 °C(Press: 0.5 Torr)
• 密度：
  1.17±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4a-methyl-2,5-dioxo-2,3,4,4a,5,6,7,8-octahydro-[1]naphthoic acid ethyl ester 在 sodium tetrahydroborate 、 cerium(III) chloride 、 对甲苯磺酸 作用下， 以 乙醇 、 苯 为溶剂， 反应 6.0h， 生成 Agn-PC-01A9DV
  参考文献：
  名称：

  抗炎剂（-）-棘酸的对映选择性合成。

  摘要：

  描述了有效的抗炎药（-）-棘酸（1）的对映选择性合成。成功的策略与（-）-Wieland-Miescher酮（10）背离，后者易于以两种对映体形式使用，构成了向完全功能化的AB环系统1的起点。 A环的C4中心，生成化合物32为单个立体异构体。C环1的构建是通过含硫二烯43与甲基丙烯醛（36）之间的Diels-Alder反应完成的，脱硫和进一步官能化后生成合成的棘酸。

  DOI：

  10.1021/jo0159035
• 作为产物：
  描述：

  3-羟基-4-戊烯酸乙酯 在 potassium fluoride 、 jones reagent 作用下， 以 甲醇 、 丙酮 为溶剂， 反应 22.0h， 生成 4a-methyl-2,5-dioxo-2,3,4,4a,5,6,7,8-octahydro-[1]naphthoic acid ethyl ester
  参考文献：
  名称：

  抗炎剂（-）-棘酸的对映选择性合成。

  摘要：

  描述了有效的抗炎药（-）-棘酸（1）的对映选择性合成。成功的策略与（-）-Wieland-Miescher酮（10）背离，后者易于以两种对映体形式使用，构成了向完全功能化的AB环系统1的起点。 A环的C4中心，生成化合物32为单个立体异构体。C环1的构建是通过含硫二烯43与甲基丙烯醛（36）之间的Diels-Alder反应完成的，脱硫和进一步官能化后生成合成的棘酸。

  DOI：

  10.1021/jo0159035

文献信息

• Stereoselective Synthesis of the ABC Ring System of Norzoanthamine
  作者：Subhash Ghosh、Fatima Rivas、Derek Fischer、Miguel A. González、Emmanuel A. Theodorakis

  DOI：10.1021/ol036492c

  日期：2004.3.1

  [reaction: see text] An efficient synthesis of enone 4, representing the ABC ring motif of norzoanthamine, is presented. The crucial C22 quaternary center was introduced via a stereoselective methylation of enone 8. The trans-anti-trans relative configuration of the ABC framework of 4 was installed via a sequence of reactions that included a hydroboration and a modified Robinson annulation.

  [反应：见正文]提出了一种有效的合成烯酮4的方法，它代表去甲乙胺的ABC环基序。关键的C22季中心通过烯酮8的立体选择性甲基化引入。ABC骨架4的反-反-反相对构型是通过一系列反应（包括硼氢化和改良的Robinson环化反应）安装的。
• Ethyl 5-[(4-Methylphenyl)sulfonyl]-3-Oxopentanoate: A Bench-Stable Synthon for Ethyl 3-Oxopent-4-enoate (Nazarov’s Reagent)
  作者：Carmela De Risi、Simonetta Benetti、Stefano Carli、Gian Pollini、Augusto Veronese、Vinicio Zanirato

  DOI：10.1055/s-0028-1083378

  日期：——

  p-toluenesulfinate to both acrylonitrile or acrylic acid were efficiently transformed through a two-step, high-yielding sequence into ethyl 5-[(4-methylphenyl)sulfonyl]-3-oxopentanoate, a convenient source for the popular Nazarov's reagent, ethyl 3-oxopent-4-enoate, which could be generated in situ by base-induced β-elimination and used for annulation reactions.

  对甲苯亚磺酸钠与丙烯腈或丙烯酸的容易获得的加合物通过两步高产序列有效地转化为 5-[(4-甲基苯基)磺酰基]-3-氧代戊酸乙酯，这是一种方便的来源流行的 Nazarov 试剂，3-oxopent-4-enoate 乙酯，它可以通过碱诱导的 β-消除原位生成并用于环化反应。
• Effect of C-9 Substituents on the Regioselectivity of A-Ring Reactions in Derivatives of the Wieland-Miescher Ketone
  作者：Kwangyong Park、William J. Scott、David F. Wiemer

  DOI：10.1021/jo00100a037

  日期：1994.10

  The nature of C-9 substituents Was found to have a significant influence on the regio- and stereochemistry of A-ring reactions in a variety of Wieland-Miescher ketone derivatives. For example, Pd-catalyzed hydrogenation of the C-9 dioxolanes resulted in much better selectivity for the cis-funded products vis-a-vis the corresponding C-9 ketone, with the parent Wieland-Miescher ketone itself and both C-4 methyl and C-4 carboalkoxy substituted analogues. In addition, methylation and acylation of A-ring enolates favored the C-2 isomer when a C-9 dioxolane group was present, but the C-4 substituted isomer was predominant with the corresponding C-9 ketone. These differences in regiochemistry may allow selective elaboration of cis-fused decalins during preparation of complex natural products.
• Sanchez, Ignacio H.; Larraza, Maria Isabel; Brena, Francisco Kuri, Synthetic Communications, 1986, vol. 16, # 3, p. 299 - 308
  作者：Sanchez, Ignacio H.、Larraza, Maria Isabel、Brena, Francisco Kuri、Cruz, Adrian、Sotelo, Octavio、Flores, Humberto J.

  DOI：——

  日期：——
• Application of the Nickel-Mediated Neopentyl Coupling in the Total Synthesis of the Marine Natural Product Arenarol
  作者：Anthony T. Watson、Kwangyong Park、David F. Wiemer、William J. Scott

  DOI：10.1021/jo00121a030

  日期：1995.8

  Racemic arenarol (1) has been synthesized from the known decalin 5 beta-carbethoxy-1,1-(1,2-ethylenedioxy)-5 alpha,8a beta-dimethyl-1,2,3,5,6,7,8,8a-octahydro-6-oxonaphthalene (9) via a short, efficient, and highly stereocontrolled sequence. Key steps in this synthesis are the directed hydrogenation of an unsaturated neopentyl alcohol to provide stereocontrolled formation of the two adjacent tertiary centers and subsequent elaboration of the arenarol skeleton via a nickel-mediated coupling of the corresponding neopentyl iodide. This sequence demonstrates the value of nickel-mediated cross-coupling reactions for carbon-carbon bond formation at neopentyl centers.