(+/-)-3,4,8,8a-tetrahydro-8a-methyl-5-methoxycarbonyl-1,6(2H,7H)-naphthalenedione | 97025-02-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-3,4,8,8a-tetrahydro-8a-methyl-5-methoxycarbonyl-1,6(2H,7H)-naphthalenedione
• 英文别名: methyl (4aS*)-4a-methyl-2,5-dioxo-3,4,4a,6,7,8-hexahydronaphthalenecarboxylate；methyl 4a-methyl-2,5-dioxo-4,6,7,8-tetrahydro-3H-naphthalene-1-carboxylate
• CAS: 97025-02-0
• 化学式: C₁₃H₁₆O₄
• 分子量: 236.268
• InChiKey: NCIRYIJZVVTTDL-UHFFFAOYSA-N

物化性质

• 熔点：
  68-70 °C
• 沸点：
  389.8±42.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 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：

  (+/-)-3,4,8,8a-tetrahydro-8a-methyl-5-methoxycarbonyl-1,6(2H,7H)-naphthalenedione 在 lithium aluminium tetrahydride 、 四溴化碳 、 三正丁基氢锡 、 对甲苯磺酸 、 乙二醇 、 三苯基膦 作用下， 生成 5,8a-二甲基-3,4,8,8a-四氢-1,6-(2H,7H)-萘二酮
  参考文献：
  名称：

  Microbiologically modified chiral synthon. I. 3,8-Dioxo-4-methoxycarbonyl-9-methyl-.DELTA.4(10)-octalin for formal total syntheses of certain sesquiterpenoids and diterpenoids.

  摘要：

  利用各种酵母对原手性 3，8-二氧代-4-甲氧羰基-9-甲基-Δ4(10)-辛卡林（1ab）进行了微生物还原。(+)-(8S)-羟基-4-甲氧基羰基-(9S)-甲基-3-氧代-Δ4(10)-辛卡林（2a）是某些倍半萜类化合物（如 α-钙）正式全合成所需的手性合成物。使用汉森藻（Hansenula anomala）等经过严格筛选的微生物，可以获得高光学纯度（>99% ee）的这种酮醇。另一种光学纯度很高的手性合成物，即 3，8-二氧代-4-甲氧基羰基-(9R)-甲基-Δ4(10)-辛烷（1b），也可用于正式全合成雌烯型二萜，如唑那洛。

  DOI：

  10.1248/cpb.37.712
• 作为产物：
  描述：

  β-Ethoxy-propionylessigsaeure-methylester 在 potassium fluoride 、 对甲苯磺酸 作用下， 以 甲醇 为溶剂， 生成 (+/-)-3,4,8,8a-tetrahydro-8a-methyl-5-methoxycarbonyl-1,6(2H,7H)-naphthalenedione
  参考文献：
  名称：

  A stereoselective synthesis of racemic andrographolide lactone

  摘要：

  DOI：

  10.1021/ja01013a028

文献信息

• Skeletal Rearrangement via Alkoxy Radical: Conversion of Epoxydecalin Thiocarbonylimidazolides to Bicyclo[6.3.0]undecanones and Bicyclo[5.3.1]undecanones
  作者：You-Ichirou Kakimoto、Yukie Ogasawara、Atsushi Nishida、Norio Kawahara、Mayumi Nishida、Hiroaki Takayanagi

  DOI：10.1016/s0040-4020(00)00635-9

  日期：2000.9

  The skeletal rearrangement of five types of epoxydecalin thiocarbonylimidazolides was investigated. This reaction proceeded via a 10-membered cyclic carbon radical formed by β-cleavage of alkoxy radicals, and produced two types of skeletal rearranged products; i.e. bicyclo[6.3.0]undecanones and bicyclo[5.3.1]undecanones. The ratio of the products strongly depended on the character and stereochemistry

  研究了五种环氧十氢化萘硫羰基咪唑啉化物的骨架重排。该反应通过由烷氧基的β-裂解形成的10元环碳自由基进行，并产生两种类型的骨架重排产物。即双环[6.3.0]十一烷和双环[5.3.1]十一烷。产物的比例在很大程度上取决于取代基的特性和立体化学。
• Immobilization of yeast and the function of immobilized yeast.
  作者：Norihiko SAITO、Haruma KAWAGUCHI、Yasuji OHTSUKA、Nobuko SHIMIZU、Seiichi INAYAMA

  DOI：10.1248/cpb.39.3085

  日期：——

  Hansenula anomala, which catalyzes an asymmetric reduction, was immobilized in bulk or spherical crosslinked polymers. The catalytic activity of the yeast for the enantio-selective reduction of 3, 8-dioxo-4-methoxycarbonyl-9-methyl-Δ4(10)-octalin (1ab) was severely affected by the immobilization conditions, such as the crosslink density, and by hydrophobicity of polymers and other components used for immobilization, oxygen concentration in the medium, etc. In some immobilized systems, the ratio of resulting enantiomers was inverted from that in a free yeast system.

  将能催化不对称还原的汉逊酵母固定在块状或球状交联聚合物中。酵母对 3，8-二氧代-4-甲氧羰基-9-甲基-Δ4(10)-辛烷（1ab）的对映选择性还原的催化活性受到固定条件（如交联密度）、聚合物和用于固定的其他成分的疏水性、介质中氧浓度等的严重影响。在某些固定化体系中，生成的对映体的比例与游离酵母体系中的比例相反。
• Skeletal rearrangement via alkoxy radical: Conversion of epoxydecalin thiocarbonylimidazolide to bicyclo[6.3.0]undecanone and bicyclo[5.3.1]undecanone
  作者：Atsushi Nishida、You-Ichirou Kakimoto、Yukie Ogasawara、Norio Kawahara、Mayumi Nishida、Hiroaki Takayanagi

  DOI：10.1016/s0040-4039(97)01190-8

  日期：1997.8

  The radical reaction of three epoxydecalin thiocarbonylimidazolides was investigated using nBu3SnH and AIBN. Two types of rearrangement from a tenmembered cyclic carbon radical, which was formed by β-cleavage of alkoxy radicals, were observed.

  使用n Bu 3 SnH和AIBN研究了三种环氧十氢化萘硫代羰基咪唑化物的自由基反应。观察到由十元环状碳自由基的两种重排，其由烷氧基的β-裂解形成。
• Inayama, Seiichi; Shimizu, Nobuko; Ohkura, Tamiko, Chemical and pharmaceutical bulletin, 1986, vol. 34, # 6, p. 2660 - 2663
  作者：Inayama, Seiichi、Shimizu, Nobuko、Ohkura, Tamiko、Akita, Hiroyuki、Oishi, Takeshi、Iitaka, Yoichi

  DOI：——

  日期：——
• 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.

表征谱图