5α-cholest-2-en-6-one | 20281-69-0

• 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-cholest-2-en-6-one
• 英文别名: cholest-2-ene-6-one；5α-cholesten-(2)-one-(6)；5α-Cholesten-(2)-on-(6)；5a-Cholest-2-en-6-one；(5S,8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-[(2R)-6-methylheptan-2-yl]-1,4,5,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-6-one
• CAS: 20281-69-0
• 化学式: C₂₇H₄₄O
• 分子量: 384.646
• InChiKey: KAFXJFSMBIBYJX-GRFPRMRASA-N

物化性质

• 熔点：
  105-106 °C(Solv: ethanol (64-17-5))
• 沸点：
  469.2±24.0 °C(Predicted)
• 密度：
  0.964±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.7
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.89
• 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-cholest-2-en-6-one 在 四丁基溴化铵 钾硼氢 作用下， 反应 2.0h， 生成 6β-hydroxy-5α-cholest-2-ene
  参考文献：
  名称：

  硼氢化钾还原吸收到聚合物载体中的酮的立体化学效应

  摘要：

  由硼氢化钾水溶液还原3β-羟基-5α-胆甾醇-6-一（1）吸收而得的6α-醇的比例在0至90％之间变化，具体取决于所用的聚合物以及是否使用相转移催化剂加入; 其他一些酮类化合物也显示出相似的立体化学效应，当底物吸附在适当聚合物的内表面上时，最大的效应可能会出现。

  DOI：

  10.1039/c39880000310
• 作为产物：
  描述：

  3beta-乙酰氧基-5alpha-胆甾烷-6-酮 在 吡啶 、 盐酸 、 乙醇 、 sodium acetate 、 溶剂黄146 作用下， 生成 5α-cholest-2-en-6-one
  参考文献：
  名称：

  i-类固醇及其转化产物的立体化学。

  摘要：

  DOI：

  10.1021/jo01161a018

文献信息

• A Simple Synthesis of Steroidal 3α,5-Cyclo-6-ones and their Efficient Transformation to Steroidal 2-En-6-ones
  作者：Masakazu Aburatani、Tadashi Takeuchi、Kenji Mori

  DOI：10.1055/s-1987-27882

  日期：——

  Sterols 1 were converted to 3α-5-cyclo-6-ones 4 via their mesylates and subsequent oxidation. Refluxing 4 with sodium bromide/p-toluene sulfonic acid in dimethylformamide gave steroidal 2-en-6-ones 5, among which 5d is an important brassinolide intermediate.

  甾醇1通过其甲磺酸酯经氧化转化为3α-5-环-6-酮4，再将4与溴化钠/对甲苯磺酸在二甲基甲酰胺中回流，得到甾体2-烯-6-酮5，其中5d是一种重要的油菜素内酯中间体。
• Potassium borohydride reductions of immobilised ketosteroids
  作者：Josie C Briggs、Philip Hodge、Zhengpu Zhang

  DOI：10.1016/s0040-4020(97)00011-2

  日期：1997.3

  insoluble supports (powdered polyethylene, microporous 2% crosslinked polystyrene beads, macroporous highly crosslinked polystyrene beads, silica gel and alumina) can be reduced using aqueous potassium borohydride. The use of phase transfer catalysts generally raises yields. In the case of 6-ketosteriods the supported reactions often follow a stereochemical course significantly different from that of

  可以使用硼氢化钾水溶液还原吸收到各种不溶性载体（粉状聚乙烯，2％交联的微孔聚苯乙烯微珠，大孔高度交联的聚苯乙烯微珠，硅胶和氧化铝）中的酮类固醇。相转移催化剂的使用通常提高产率。对于6-酮类化合物，所支持的反应通常遵循的立体化学过程与溶液中类似反应的显着不同。这归因于类固醇在载体内表面上的吸附。在这些情况下，基本上抑制了烷氧基硼氢化物对酮类固醇的还原，因此大部分还原是由BH 4-引起的。本身是一种相对空间上不需要的还原剂。最终结果是，尽管硼氢化钾可将溶液中的6-酮类固醇还原成15:85的6α-和6β-醇，但负载的类固醇的比例可高达90:10。
• Synthesis of 5.ALPHA.-cholestan-6-one derivatives with some substituents at the C-1, C-2, or C-3 position.
  作者：SUGURU TAKATSUTO、NOBUO IKEKAWA

  DOI：10.1248/cpb.35.986

  日期：——

  In order to investigate the regioselectivity of Baeyer-Villiger oxidation, thirty 5α-cholestan-6- one derivatives with various substituents (methyl, hydrogen, acetoxymethyl, methoxy, acetyloxy, benzoyloxy, trifluoroacetyloxy, p-toluenesulfonyloxy) at the C-1, C-2, or C-3 position were synthesized from cholesterol. The 6-oxo functional group of 5α-cholestan-6-one derivatives was introduced via hydroboration. The 3β-derivatives were readily obtained by using the native 3β- hydroxyl group of cholesterol. The 3α-isomers were obtained by inversion of the configuration of the 3β-tosylate 24 with tetra-n-butylammonium acetate in refluxing 2-butanone. The 2β-isomers were derived from the 2-ene 43 by bromohydrination, LiAlH4 reduction, and esterification. The 2β- to 2α-hydroxyl group inversion was achieved by Birch reduction of the 2-oxo steroid 51. The 1α-derivatives were derived from the known 6β-acetoxy- 1 α-hydroxy-5α-cholest-2-ene (57).

  为了研究拜耳-维利格氧化的区域选择性，我们从胆固醇合成了30种具有不同取代基（甲基、氢、乙酰氧甲基、甲氧基、乙酰氧基、苯甲酰氧基、三氟乙酰氧基、对甲苯磺酰氧基）在C-1、C-2或C-3位置的5α-胆甾烷-6-酮衍生物。通过氢硼化反应引入5α-胆甾烷-6-酮衍生物的6-氧功能团。通过使用胆固醇天然的3β-羟基，可以轻松得到3β-衍生物。通过在回流2-丁酮中使用四正丁基铵醋酸盐，将3β-甲苯磺酸酯24的构型反转得到3α-异构体。2β-异构体来自2-烯43通过溴氢化、LiAlH4还原和酯化反应得到。2β-到2α-羟基的反转通过2-氧甾体51的伯奇还原实现。1α-衍生物来自已知的6β-乙酰氧基-1α-羟基-5α-胆甾-2-烯（57）。
• Brassinolide and its analogs. Part IV. Synthesis of brassinolide analogs with or without the steroidal side chain.
  作者：Michitada KONDO、Kenji MORI

  DOI：10.1271/bbb1961.47.97

  日期：——

  Four brassinolide analogs were synthesized starting from cholesterol, stigmasterol or pregnenolone. An analog possessing a hydroxyl group at C-17 instead of the steroidal side chain was only 0.001% as active as brassinolide upon lamina-inclination testing with rice seedlings, while other analogs were 1-2% as active as brassinolide. This indicates the indispensable role of the side chain for the plant growth-promoting activity of brassino-steroids.

  从胆固醇、豆甾醇或孕烯醇酮出发，合成了四种黄铜内酯类似物。在对水稻秧苗进行片层倾斜试验时，一种在 C-17 处具有羟基而不是甾体侧链的类似物的活性只有黄铜内酯的 0.001%，而其他类似物的活性是黄铜内酯的 1-2%。这表明侧链对黄铜内酯的植物生长促进活性起着不可或缺的作用。
• Conformational free energy differences in steroids. Part VI. Intramolecular electrostatic interactions in 3-azidocholestan-6-ones: conformational preference of the azido-group
  作者：D. Neville Jones、K. J. Wyse、D. E. Kime

  DOI：10.1039/j39710002763

  日期：——

  Equilibrations of 3α- and 3β-azido-5α-cholestan-6-ones with their 5β-isomers were influenced by intramolecular electrostatic interactions between the azide and ketone groups. Calculated values for these interactions were in reasonable accord with the experimental findings. N.m.r. spectroscopic examination of cyclohexyl azide at –80° in carbon disulphide, [2H4]methanol, and [2H8]toluene provided a value

  3 Equilibrations α -和3β叠氮基-5- α与其5β异构体-胆甾-6-酮是由叠氮化物和酮基之间的分子内的静电相互作用的影响。这些相互作用的计算值与实验结果合理地吻合。在二硫化碳，[ 2 H 4 ]甲醇和[ 2 H 8 ]甲苯中于–80°进行环己基叠氮化物的Nmr光谱检查，可为叠氮基的构象偏爱度提供一个值。对于2 M，最准确的数字是0·80±0·06 kcal mol –1-二硫化碳溶液。讨论了叠氮基，异氰酸根基和异硫氰酸根基的构象偏好之间的差异。