(3S,8S,9S,10R,13R,14S,17R)-17-[(E,2S)-6-hydroxy-6-methylhept-3-en-2-yl]-10,13-dimethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-ol | 144124-85-6

• 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: (3S,8S,9S,10R,13R,14S,17R)-17-[(E,2S)-6-hydroxy-6-methylhept-3-en-2-yl]-10,13-dimethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-ol
• CAS: 144124-85-6
• 化学式: C₂₇H₄₄O₂
• 分子量: 400.645
• InChiKey: RXNXZBKSKJZKNN-AVDDMWLVSA-N

物化性质

• 沸点：
  518.6±25.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  [(E,2S)-2-[(3S,8S,9S,10R,13S,14S,17S)-3-[tert-butyl(dimethyl)silyl]oxy-10,13-dimethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-17-yl]-6-(1-ethoxyethoxy)-6-methylhept-3-en-2-yl] methyl carbonate 在 bis(acetylacetonato)palladium(II) 、 三丁基膦 、 4-甲基苯磺酸吡啶 甲酸 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 2.5h， 生成 (3S,8S,9S,10R,13R,14S,17R)-17-[(E,2S)-6-hydroxy-6-methylhept-3-en-2-yl]-10,13-dimethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-ol
  参考文献：
  名称：

  A novel method for stereospecific generation of either C-20 epimer in steroid side chains by palladium-catalyzed hydrogenolysis of C-20 allylic carbonates

  摘要：

  Both natural and unnatural epimers at C-20 in a steroid side chain can be generated stereospecifically by the palladium-catalyzed hydrogenolysis with triethylammonium formate of C-20 (Z) or (E) allylic carbonates, respectively.

  DOI：

  10.1021/jo00049a004

文献信息

• A novel method for stereospecific generation of natural C-17 stereochemistry and either C-20 epimer in steroid side chains by palladium-catalyzed hydrogenolysis of C-17 and C-20 allylic carbonates.
  作者：Tadakatsu Mandai、Takaji Matsumoto、Mikio Kawada、Jiro Tsuji

  DOI：10.1016/s0040-4020(01)80769-9

  日期：1994.1

  alcohol, obtained by the reaction of C-17-keto steroid with isopropenyllithium, was converted to carbonate. Its hydrogenolysis with triethylammonium formate affords C-17β-isopropenyl group. Steroid side chain units were introduced by the reaction of C-20 keto steroid with (E) and (Z) alkenyl lithiums. The natural epimer at C-20 in steroid side-chains was generated stereospecifically by the palladium-catalyzed

  通过C-17-酮类固醇与异丙烯基锂反应获得的烯丙醇被转化为碳酸酯。用甲酸三乙铵进行氢解可得到C-17β-异丙烯基。通过C-20酮类固醇与（E）和（Z）烯基锂的反应引入类固醇侧链单元。类固醇侧链中C-20的天然差向异构体是通过钯催化的C-20（Z）烯丙基碳酸三甲酸甲酸乙酯与甲酸三乙铵的氢解而立体生成的，而非天然构型则是由C-20（E）碳酸烯丙酯生成的。
• Complexation of Vinylcyclopropanes with Zirconocene−1-butene Complex:  Application to the Stereocontrolled Synthesis of Steroidal Side Chains
  作者：Susumu Harada、Hiromichi Kiyono、Ryoko Nishio、Takeo Taguchi、Yuji Hanzawa、Motoo Shiro

  DOI：10.1021/jo962064r

  日期：1997.6.13

  Reactions of vinylcyclopropane derivatives with a zirconocene-1-butene complex (''Cp2Zr'') caused regioselective cleavage of the cyclopropyl bond to give eta(3) pi-allylic and/or eta(1) sigma-allylic complexes. The regioselectivity of the bond cleavage and the formation of a eta(3) pi-allylic or eta(1) sigma-allylic complex depend on the bulkiness of the substituents on the cyclopropyl group and the presence of leaving functionality. A catalytic use of ''Cp2Zr'' in the presence of excess Grignard reagent also caused a ring opening of the vinylcyclopropane derivatives with the same sense of regiochemical selectivity. The reaction of the thermally equilibrated ''Cp2Zr''-propenylcyclopropane complex with acetone indicated the possibility for the synthesis of the steroidal side chain in either natural or unnatural forms. The synthetic utility of the present ''Cp2Zr''-vinylcyclopropane chemistry was ascertained by the stereocontrolled preparation of the C-20, C-24 dimethylated steroidal side chain which is identical to the active metabolite of vitamin D-2.