3β-hydroxy-22,23,24,25,26,27-hexanordammaran-20-one | 3819-21-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: 3β-hydroxy-22,23,24,25,26,27-hexanordammaran-20-one
• 英文别名: 3β-hydroxy-4,4,8,14-tetramethyl-18-nor-5α-pregnan-20-one；3β-Hydroxy-4,4,8,14-tetramethyl-18-nor-5α-pregnan-20-on；3β-Hydroxy-22,23,24,25,26,27-hexanor-5α-dammaranon-(20)；3β-Hydroxy-20-oxo-(22/27)-hexanor-dammaran；3β-Hydroxy-20-oxo-hexanor-dammaran；1-[(3S,5R,8R,9R,10R,13R,14R,17S)-3-hydroxy-4,4,8,10,14-pentamethyl-2,3,5,6,7,9,11,12,13,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-17-yl]ethanone
• CAS: 3819-21-4
• 化学式: C₂₄H₄₀O₂
• 分子量: 360.58
• InChiKey: GRVOAMBHUWXGTO-SXSJETLGSA-N

物化性质

• 熔点：
  194-196 °C
• 沸点：
  445.9±18.0 °C(Predicted)
• 密度：
  1.014±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  26
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3β-hydroxy-22,23,24,25,26,27-hexanordammaran-20-one 在 palladium on activated charcoal 咪唑 、 四丁基氟化铵 、 氢气 、 溴 、 sodium cyanoborohydride 、 sodium carbonate 、 溶剂黄146 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 生成
  参考文献：
  名称：

  Synthesis of dammarane-type triterpenoids with anti-inflammatory activity in vivo

  摘要：

  The 17-alpha-substituted triterpene 1 [(17alpha)-23-(E)-dammara-20,23-diene-3beta, 25-diol] showed promising activity in animal models of immunosuppression and inflammation. Using a mouse model for inflammatory skin diseases (oxazolone-induced allergic contact dermatitis, ACD) as the directing in vivo test system, Structure-activity-relation ship studies with the aim to understand the necessary structural requirements for the biological activity of 1 were conducted. Furthermore, we anticipated to identify biologically active compounds with the 17beta configuration, which are thermodynamically more stable and much easier to synthesize. This was achieved by identifying the 17-beta substituted dammarane 5(B) and its analogues. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2004.02.104
• 作为产物：
  描述：

  (2E,6E,10E,14E)-18,19-epoxy-2-isopentyloxy-6,11,15,19-tetramethylicosa-2,6,10,14-tetraene 在 Arabidopsis thaliana lupeol synthase 、 Tween-80 作用下， 以 phosphate buffer 为溶剂， 反应 13.0h， 生成 3β-hydroxy-22,23,24,25,26,27-hexanordammaran-20-one
  参考文献：
  名称：

  达玛烯基阳离子的结构和反应性：三萜烯合成中的构型传递。

  摘要：

  达玛烯基阳离子（13）是氧化角鲨烯环化成植物中各种次级三萜代谢物的最后一个常见中间体。我们研究了13的结构和反应性，以了解控制三萜合成的区域和立体特异性的因素。首先，我们通过将底物类似物（18 E）-22,23-dihydro-20-oxaoxidosqualene（21）与不含酵母的重组酵母菌株中的LUP1一起孵育，证明13在拟南芥狼毒醇合成酶（LUP1）中具有17β侧链。其他环化酶并显示21的唯一产物为3β-羟基-22,23,24,25,26,27-hexanor-17β-dammaran-20-one。在气相模型上进行了量子力学计算，结果表明20-氧杂取代对底物结合和导致C17差向异构体13的反应活化能的影响可忽略不计。进一步的分子建模表明，由于环化酶活性位点腔中的旋转自由度有限，四环中间体13的C17构型可以从五环或6--6-6-6四环产物的角甲基构型推导。构型传递的这一规则有助于

  DOI：

  10.1021/jo050147e

文献信息

• Préparation de la 8,14-diméthyl 18-nor-testostérone
  作者：Pierre Crabbé、Guy Ourisson、Takeyoshi Takahashi

  DOI：10.1016/0040-4020(58)80024-1

  日期：1958.1

  A tetracyclic triterpene has been isolated from the oleoresins of four Dipterocarpus species. It has been identified with van Itallie's dipterocarpol and Mills' hydroxy-dammarenone-II (I). The side chain of dipterocarpol has been degraded to the methyl ketone (VII, R = H, by three different methods. Trifluoroperacetic acid converted the ketone into the 17-acetate (XXII, R = H, R′ = Ac), and ring A

  从四个双翅类属植物的油性树脂中分离出了四环三萜。它已被范·伊塔利（van Itallie）的二萜卡普尔和米尔斯（Mills）的羟基-达马利酮-II（I）鉴定。二萜的侧链已通过三种不同的方法降解为甲基酮（VII，R = H），三氟过氧乙酸将酮转化为17-乙酸酯（XXII，R = H，R'= Ac），且环A然后通过经典方法将其修饰为药理学上无活性的睾丸激素类似物（XXX，R = H），并讨论了双萜的立体化学。
• Isolation and synthesis of a novel immunosuppressive 17α-substituted dammarane from the flour of the Palmyrah palm (Borassus flabellifer)
  作者：L. Révész、P. Hiestand、L. La Vecchia、R. Naef、H.-U. Naegeli、L. Oberer、H.-J. Roth

  DOI：10.1016/s0960-894x(99)00220-6

  日期：1999.6

  The novel triterpene 1 with a dammarane skeleton and a hitherto unknown 17alpha-substitution pattern has been isolated from the Palmyrah palm in low yield and prepared by synthesis in larger quantities. 1 was shown to be an extremely potent immunosuppressant in vitro (MLR; IC50 = 10 ng/ml) and in vivo (DTH; ED50 = 0.01 mg/kg p.o.). A glucocorticoid like activity is excluded.

  从丹葵棕榈中分离出具有丹玛烷骨架和迄今未知的17α-取代模式的新型三萜1，并通过大量合成制备。1在体外（MLR; IC50 = 10 ng / ml）和体内（DTH; ED50 = 0.01 mg / kg po）被证明是一种非常有效的免疫抑制剂。排除类似糖皮质激素的活性。
• 3β-Hydroxyhexanordammaran-20-one from Euphorbia supina
  作者：Reiko Tanaka (neé Morita)、Minako Matsuda、Shunyo Matsunaga

  DOI：10.1016/s0031-9422(00)82513-3

  日期：1987.1

  Abstract A new tetracyclic hexanortriterpene ketol, 3β-hydroxy-22,23,24,25,26,27-hexanordammaran-20-one, has been isolated from the whole herb of Euphorbia supina .

  摘要 从大戟全草中分离得到一种新的四环六降三萜酮醇，3β-羟基-22,23,24,25,26,27-hexanordammaran-20-one。
• The Fluorine Atom as a Cation-Stabilizing Auxiliary in Biomimetic Polyene Cyclizations:  Total Synthesis of <i>dl</i>-Dammarenediol¹
  作者：William S. Johnson、William R. Bartlett、Boris A. Czeskis、Arnaud Gautier、Cheol H. Lee、Rémy Lemoine、Eric J. Leopold、Gregory R. Luedtke、Katherine J. Bancroft

  DOI：10.1021/jo991196s

  日期：1999.12.1

  Dammarenediols I (1a) and II (1b) were prepared by an efficient nonenzymatic biomimetic polyene tetracyclization route. The cyclization substrate, pentaenol 3, contains a tetramethylallylic alcohol initiator, an allyltrimethylsilane terminating group, and a fluorine atom at pro-C-13 to serve as a cation-stabilizing (C-S) auxiliary controlling the regiochemistry of the C/D ring juncture. The synthesis of 3 employed lithium-halogen exchange to create alcohols 10 and 19. The Z-fluoroalkene in 3 was introduced stereoselectively via the Trost palladium-catalyzed alkylation of allylic acetate 11 (Z/E: 4.6/1). The cyclization of 3 was most efficient (62% isolated yield) when it was added as a dilute solution in dichloromethane to trifluoroacetic acid at -45 degrees C to afford tetracyclic fluoro diene 24 possessing the trans-anti-trans-anti-trans ring stereochemistry of the dammaranes. Replacement of the fluorine atom of 24 with hydrogen with complete retention of configuration was accomplished using the Ohsawa-Oishi reagent (Na/K alloy and crown ether). Wacker oxidation of the resulting hydrocarbon provided ketone 28, which after ketalization was ozonolyzed with a reductive workup to give the SP-alcohol 30. Ketal hydrolysis followed by Grignard reaction with isopentenylmagnesium bromide afforded the dammarenediols (1/3, 1a/1b).
• 429. The constitution of the neutral, tetracyclic triterpenes of dammar resin
  作者：J. S. Mills

  DOI：10.1039/jr9560002196

  日期：——