3β-p-toluenesulfonyl-5α-cholest-6-one | 83456-32-0

• 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: 3β-p-toluenesulfonyl-5α-cholest-6-one
• 英文别名: 3β-p-toluenesulfonyloxy-5α-cholestan-6-one；3β-(toluene-4-sulfonyloxy)-5α-cholestan-6-one；3β-(Toluol-4-sulfonyloxy)-5α-cholestan-6-on；3β-(Toluol-sulfonyl-(4)-oxy)-5α-cholestanon-(6)；[(3S,5S,8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-[(2R)-6-methylheptan-2-yl]-6-oxo-1,2,3,4,5,7,8,9,11,12,14,15,16,17-tetradecahydrocyclopenta[a]phenanthren-3-yl] 4-methylbenzenesulfonate
• CAS: 83456-32-0
• 化学式: C₃₄H₅₂O₄S
• 分子量: 556.85
• InChiKey: QBGOILXRKWNSDI-RQFVFKLTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.8
• 重原子数：
  39
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  68.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3β-p-toluenesulfonyl-5α-cholest-6-one 在 吡啶 、 sodium tetrahydroborate 、 三氯氧磷 作用下， 生成 3α-Thiocyanato-cholesten-(5)
  参考文献：
  名称：

  Bourdon, Bulletin de la Societe Chimique de France, 1958, p. 1117

  摘要：

  DOI：
• 作为产物：
  描述：

  6-硝基胆固醇乙酸酯 在 吡啶 、 盐酸 、 乙醇 、 溶剂黄146 、 锌 作用下， 生成 3β-p-toluenesulfonyl-5α-cholest-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

• 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）。
• 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。
• Remote substituent effect on the regioselectivity in the baeyer-villiger oxidation of 5α-cholestan-6-one derivatives
  作者：Suguru Takatsuto、Nobuo Ikekawa

  DOI：10.1016/s0040-4039(00)81564-6

  日期：——

  The regioselectivity in the Baeyer-Villiger oxidation of 5α-cholestan-6-one derivatives was markedly affected by the substituents at C-1, 2 or 3 position which were located at γ or δ position from the reaction center c-6.

  5α-胆甾烷-6-一衍生物在Baeyer-Villiger氧化中的区域选择性受到位于距反应中心c-6的γ或δ位置的C-1、2或3位取代基的显着影响。
• Zur Synthese des Ecdysons. II. Mitteilung über Insektenhormone Synthesen von 2β, 3β-Dihydroxy-6-keto-A|B-<i>cis</i>-Steroiden
  作者：R. Wiechert、U. Kerb、P. Hocks、A. Furlenmeier、A. Fürst、A. Langemann、G. Waldvogel

  DOI：10.1002/hlca.19660490517

  日期：——

  Experiments towards a synthesis of ecdysone (1) ([22R]-2β, 3β, 14, 22, 25-pentahydroxy-5β, 14α-cholest-7-en-6-one) have led to 2β, 3β-dihydroxy-6-keto-5α-steroids. These could be epimerized to the corresponding 5β-series. The proposed configurational assignments are supported by physical data and chemical correlation.

  合成蜕皮激素（1）（[22 R ]-2β，3β，14，22，25-五羟基-5β，14α-胆甾-7-en-6-one）的实验已导致2β，3β-二羟基- 6-酮5α-类固醇。这些可以差向异构为相应的5β系列。物理数据和化学相关性为所建议的构型分配提供了支持。
• Barton, Derek H. R.; Boivin, Jean; Hill, Christopher H., Journal of the Chemical Society. Perkin transactions I, 1986, p. 1797 - 1804
  作者：Barton, Derek H. R.、Boivin, Jean、Hill, Christopher H.

  DOI：——

  日期：——