(5α,13α,17α)-10,17-dimethylgonan-16-one | 1314110-69-4

• 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: (5α,13α,17α)-10,17-dimethylgonan-16-one
• 英文别名: 17α-methyl-5α-androst-16-one；(5R,8S,9S,10S,13R,14S,17S)-10,17-dimethyl-2,3,4,5,6,7,8,9,11,12,13,14,15,17-tetradecahydro-1H-cyclopenta[a]phenanthren-16-one
• CAS: 1314110-69-4
• 化学式: C₁₉H₃₀O
• 分子量: 274.447
• InChiKey: SDCYHTYCHREFRR-HPTIQJPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (5α,13α,17α)-10,17-dimethylgonan-16-one 在 一水合肼 、 potassium hydroxide 作用下， 以 甲苯 、 二乙二醇 为溶剂， 反应 21.0h， 以32%的产率得到17α-methyl-18-nor-13α-androstane
  参考文献：
  名称：

  原油中化石甾烷生物标志物的鉴定 - 具有改性碳骨架的雄甾烷

  摘要：

  制备了雄烷的三种结构异构体，用于与来自阿曼的地质样品中的三种未知的化石 C19H32 有机生物标志物（洗脱顺序为“19A”、“19B”和“19C”）进行比较。3β-甲基-A-去甲雄甾烷由睾酮分六步制备（总产率为8%）。该序列的关键步骤是 A 环的 Eschenmoser 断裂和再循环。3-甲基-A-去甲雄甾烷的四种立体异构体的混合物（4%总产率）是通过在三个步骤中的A环再环化之后的烯烃的离子氢化来制备的。17-Methyl-18-nor-androstane 是由二氢睾酮合成的异构体混合物（58% 的总产率），以 13β-甲基向 C-17 的 Wagner-Meerwein 转变为关键步骤，分四步合成。纯 17β- 和 17α-methyl-18-nor-13α-androstane（总产率为 4% 和 2%，分别）在 Wagner-Meerwein 重排产物的 α-氧化和随后的还原后的三

  DOI：

  10.1002/ejoc.201300788
• 作为产物：
  描述：

  雄诺龙 在 吡啶 、 chromium(VI) oxide 、 4-二甲氨基吡啶 、 palladium 10% on activated carbon 、 乙基溴化镁 、 氢气 、 一水合肼 、 potassium hydroxide 作用下， 以 吡啶 、 乙醚 、 二氯甲烷 、 乙酸乙酯 、 甲苯 、 二乙二醇 为溶剂， 20.0~220.0 ℃ 、400.01 kPa 条件下， 反应 224.0h， 生成 (5α,13α,17α)-10,17-dimethylgonan-16-one
  参考文献：
  名称：

  原油中化石甾烷生物标志物的鉴定 - 具有改性碳骨架的雄甾烷

  摘要：

  制备了雄烷的三种结构异构体，用于与来自阿曼的地质样品中的三种未知的化石 C19H32 有机生物标志物（洗脱顺序为“19A”、“19B”和“19C”）进行比较。3β-甲基-A-去甲雄甾烷由睾酮分六步制备（总产率为8%）。该序列的关键步骤是 A 环的 Eschenmoser 断裂和再循环。3-甲基-A-去甲雄甾烷的四种立体异构体的混合物（4%总产率）是通过在三个步骤中的A环再环化之后的烯烃的离子氢化来制备的。17-Methyl-18-nor-androstane 是由二氢睾酮合成的异构体混合物（58% 的总产率），以 13β-甲基向 C-17 的 Wagner-Meerwein 转变为关键步骤，分四步合成。纯 17β- 和 17α-methyl-18-nor-13α-androstane（总产率为 4% 和 2%，分别）在 Wagner-Meerwein 重排产物的 α-氧化和随后的还原后的三

  DOI：

  10.1002/ejoc.201300788

文献信息

• Synthesis of novel 13α-18-nor-16-carboxamido steroids via a palladium-catalyzed aminocarbonylation reaction
  作者：Eszter Szánti-Pintér、Zsolt Csók、Zoltán Berente、László Kollár、Rita Skoda-Földes

  DOI：10.1016/j.steroids.2013.08.011

  日期：2013.12

  13α-18-nor-16-Carboxamido steroids were synthesized via a palladium-catalyzed aminocarbonylation reaction of the corresponding iodoalkenes. The starting material was an unnatural 13α-16-keto steroid, obtained by a Wagner-Meerwein rearrangement of a 16α,17α-epoxide in the presence of [BMIM][BF4]. The 13α-16-keto steroid was converted to a mixture of 16-iodo-16-ene and 16-iodo-15-ene derivatives in two

  13α-18-nor-16-Carboxamido 类固醇是通过钯催化的相应碘代烯烃的氨基羰基化反应合成的。起始材料是一种非天然的 13α-16-酮类固醇，在 [BMIM][BF4] 存在下通过 16α,17α-环氧化物的 Wagner-Meerwein 重排获得。13α-16-酮类固醇通过巴顿方法分两步转化为 16-iodo-16-ene 和 16-iodo-15-ene 衍生物的混合物。使用不同的伯胺和仲胺作为亲核试剂进行甾体烯基碘化物的氨基羰基化。以良好的收率获得了产物 16-carboxamido-16-ene 和 16-carboxamido-15-ene 衍生物，并通过 (1)H 和 (13)C NMR、IR 和 MS 对其进行了表征。上述两种不饱和甲酰胺的还原产生相同的产物，17α-甲基-16α-甲酰胺-雄甾烷。
• Diols Speed Up Guanidine Base Catalyzed Claisen‐Schmidt Condensation to Produce New 15‐Arylidene Steroids
  作者：Dávid Ispán、Áron Küzdő、Máté Fonyó、Ágnes Gömöry、Nikolay Tumanov、Johan Wouters、Sándor Mahó、György Lendvay、Rita Skoda‐Földes

  DOI：10.1002/ejoc.202300560

  日期：2023.9.6

  Diols are efficient co-catalysts in guanidine catalysed condensation of ketones and aldehydes. According to quantum chemical calculations the acceleration effect can be explained by the formation of complexes of carbonyl compounds and diols held together by double H-bonding. The base/diol mixture can be separated from the product and recycled by reversible CO2 capture and release.

  二醇是胍催化的酮和醛缩合反应中的有效助催化剂。根据量子化学计算，加速效应可以通过羰基化合物和二醇通过双氢键结合在一起形成复合物来解释。碱/二醇混合物可以从产物中分离出来，并通过可逆的CO 2捕获和释放进行回收。
• Synthesis of novel 13α-18-norandrostane–ferrocene conjugates via homogeneous catalytic methods and their investigation on TRPV1 receptor activation
  作者：Eszter Szánti-Pintér、Johan Wouters、Ágnes Gömöry、Éva Sághy、Éva Szőke、Zsuzsanna Helyes、László Kollár、Rita Skoda-Földes

  DOI：10.1016/j.steroids.2015.10.016

  日期：2015.12

  13 alpha-Steroid-ferrocene derivatives were synthesized via two reaction pathways starting from an unnatural 16-keto-18-nor-13 alpha-steroid. The unnatural steroid was converted to ferrocene derivatives via copper-catalyzed azide-alkyne cycloaddition or palladium-catalyzed aminocarbonylation. 16-Azido- and 16-N-(prop-2-ynyl)-carboxamido-steroids were synthesized as starting materials for azide-alkyne cycloaddition with the appropriate ferrocene derivatives. Based on our earlier work, aminocarbonylation of 16-iodo-16-ene and 16-iodo-15-ene derivatives was studied with ferrocenylmethylamine. The new products were obtained in moderate to good yields and were characterized by H-1 and C-13 NMR, IR and MS. The solid state structure of the starting material 13 alpha-18-norandrostan-16-one and two carboxamide products were determined by X-ray crystallography. Evidences were provided that the N-propargyl-carboxamide compound as well as its ferrocenylmethyltriazole derivative are able to decrease the activation of TRPV1 receptor on TRG neurons. (C) 2015 Elsevier Inc. All rights reserved.
• Ionic Liquid-Promoted Wagner–Meerwein Rearrangement of 16α,17α-Epoxyandrostanes and 16α,17α-Epoxyestranes
  作者：Anita Horváth、Ágota Szájli、Róbert Kiss、János Kóti、Sándor Mahó、Rita Skoda-Földes

  DOI：10.1021/jo2006285

  日期：2011.8.5

  Ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate ([bmitn](+)[PF(6)](-)) and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim](-)(+)[BF(4)](-)) were found to promote an unusual Wagner-Meerwein rearrangement of steroidal 16 alpha,17 alpha-epolddes leading to unnatural 13-epi-18-nor-16-one derivatives as the main products. These compounds were isolated in good to excellent yields. 16 alpha-Hydroxy-Delta(13)-18-norsteroid5, the results of the usual rearrangement, were obtained as minor components of the reaction mixtures. The ionic liquid [bmim](+)[PF(6)](-) was shown to induce C-ring aromatization of 16 alpha,17 alpha-epoxyestranes due to the formation of HF, the hydrolysis product of [PF(6)](-). Increasing amounts of HF and [PO(2)F(2)](-) were detected by (19)F and (31)P NMR when the ionic liquid was reused. The structures of the steroidal products, 16-oxo-18-nor-13 alpha-steroid derivatives, 16 alpha-hydroxy-Delta(13)-18-norsteroids, and C-aromatic compounds were determined by two-dimensional NMR techniques and high-resolution mass spectrometry (HRMS). The ionic liquids were recirculated efficiently.
• Identification of a Fossil Sterane Biomarker in Crude Oil - an Androstane with a Modified Carbon Skeleton
  作者：Matthias Bender、Marc Schmidtmann、Jürgen Rullkötter、Roger E. Summons、Jens Christoffers

  DOI：10.1002/ejoc.201300788

  日期：2013.9

  of four stereoisomers of 3-methyl-A-nor-androstane (4 % overall yield) was prepared by ionic hydrogenation of the olefin after A-ring recyclization in three steps. 17-Methyl-18-nor-androstane was synthesized in four steps as a mixture of isomers (58 % overall yield) from dihydrotestosterone with a Wagner–Meerwein shift of the 13β-methyl group to C-17 as the key step. Pure 17β- and 17α-methyl-18-nor-13α-androstane

  制备了雄烷的三种结构异构体，用于与来自阿曼的地质样品中的三种未知的化石 C19H32 有机生物标志物（洗脱顺序为“19A”、“19B”和“19C”）进行比较。3β-甲基-A-去甲雄甾烷由睾酮分六步制备（总产率为8%）。该序列的关键步骤是 A 环的 Eschenmoser 断裂和再循环。3-甲基-A-去甲雄甾烷的四种立体异构体的混合物（4%总产率）是通过在三个步骤中的A环再环化之后的烯烃的离子氢化来制备的。17-Methyl-18-nor-androstane 是由二氢睾酮合成的异构体混合物（58% 的总产率），以 13β-甲基向 C-17 的 Wagner-Meerwein 转变为关键步骤，分四步合成。纯 17β- 和 17α-methyl-18-nor-13α-androstane（总产率为 4% 和 2%，分别）在 Wagner-Meerwein 重排产物的 α-氧化和随后的还原后的三