4-((phenylthio)methyl)-4-pregnene-3,20-dione 20-ethylene ketal | 146201-22-1

• 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: 4-((phenylthio)methyl)-4-pregnene-3,20-dione 20-ethylene ketal
• 英文别名: (8S,9S,10R,13S,14S,17S)-10,13-dimethyl-17-(2-methyl-1,3-dioxolan-2-yl)-4-(phenylsulfanylmethyl)-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-3-one
• CAS: 146201-22-1
• 化学式: C₃₀H₄₀O₃S
• 分子量: 480.712
• InChiKey: SJESDDAIITTWGB-SGFQXBSMSA-N

物化性质

• 沸点：
  585.9±50.0 °C(predicted)
• 密度：
  1.18±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  34
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  60.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-((phenylthio)methyl)-4-pregnene-3,20-dione 20-ethylene ketal 在 吡啶 、 盐酸 、 sodium hydroxide 、 lithium aluminium tetrahydride 、 偶氮二异丁腈 、 n-Bu₄SnH 、 氨 、 双氧水 、 lithium 、 potassium 2-methylbutan-2-olate 、 溶剂黄146 、 三乙胺 、 sodium iodide 、 diborane(6) 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 丙酮 、 苯 为溶剂， 反应 7.0h， 生成 (20R,23R,24S)-5α-Dinosterane
  参考文献：
  名称：

  5α-地甾烷的C-23和C-24非对映异构体的合成

  摘要：

  制备C 30生物标记物5α-地甾烷（1）的C-23和C-24非对映异构体的立体选择路线涉及（20S）-20-（碘甲基）-4α-甲基-5α-孕烯（7）与3,4-二甲基戊酸甲酯饱和酯（9）结合，然后还原，主要得到赤型-非对映异构体或7，与α，β-不饱和酯3,4-二甲基戊烯酸甲酯烷基化（12）），然后还原，主要得到苏-非对映异构体。

  DOI：

  10.1016/0040-4039(93)88018-e
• 作为产物：
  描述：

  孕烯醇酮 在 N-甲基-4-哌啶酮 、 aluminum isopropoxide 、 对甲苯磺酸 、 三乙胺 作用下， 生成 4-((phenylthio)methyl)-4-pregnene-3,20-dione 20-ethylene ketal
  参考文献：
  名称：

  5α-地甾烷的C-23和C-24非对映异构体的合成

  摘要：

  制备C 30生物标记物5α-地甾烷（1）的C-23和C-24非对映异构体的立体选择路线涉及（20S）-20-（碘甲基）-4α-甲基-5α-孕烯（7）与3,4-二甲基戊酸甲酯饱和酯（9）结合，然后还原，主要得到赤型-非对映异构体或7，与α，β-不饱和酯3,4-二甲基戊烯酸甲酯烷基化（12）），然后还原，主要得到苏-非对映异构体。

  DOI：

  10.1016/0040-4039(93)88018-e

文献信息

• Synthesis of biological markers in fossil fuels. 7. Selected diastereomers of 4.alpha.-methyl-5.alpha.-stigmastane and 5.alpha.-dinosterane
  作者：Ivan Stoilov、Ewa Kolaczkowska、David S. Watt、Jan St. Pyrek、Robert M. K. Carlson、Frederick J. Fago、J. Michael Moldowan

  DOI：10.1021/jo00064a039

  日期：1993.6

  Efficient routes for the preparation of selected C-23 and C-24 diastereomers of the C30 biological markers 4alpha-methyl-5alpha-stigmastane (1) and 5alpha-dinosterane (2) involved the alkylation of 20-(iodomethyl)-4alpha-methyl-5alpha-pregnane with either saturated or alpha,beta-unsaturated esters. The alkylation of (20S)-20-(iodomethyl)-4alpha-methyl-5alpha-pregnane with methyl (3R)-3-ethyl-4-methylpentanoate furnished methyl (20R,23zeta,24S)-4alpha-methyl-5alpha-stigmastane-23-carboxylate, and a subsequent decarbomethoxylation provided (20R,24R)-l. The alkylation of (20S)-20-(iodomethyl)-4alpha-methyl-5alpha-pregnane with methyl (3S)-3,4-dimethylpentanoate led to methyl (20R,23zeta,24R)-4alpha,24-dimethyl-5alpha-cholestane-23-carboxylate, and the reduction of this mixture provided principally (20R,23S,24R)-5alpha-dinosteran-29-ol. The further reduction of the mesylate of this isomer secured (20R,23S,24R)-5alpha-dinosterane (2a). The application of the same sequence of reactions using methyl (3R)-3,4-dimethylpentanoate led principally to (20R,23R,24S)-5alpha-dinosterane (2d). The alkylation of (20S)-20-(iodomethyl)-4alpha-methyl-5alpha-pregnane with methyl (2zeta)-3,4-dimethyl-2-pentanoate and a subsequent reduction of the ester provided a separable mixture of (20R,23R)- and (20R,23S)-5alpha-dinoster-24-(28)-en-29-ol in a 2.4:1 ratio. The conversion of (20R,23R)-5alpha-dinoster-24(28)-en-29-ol to the corresponding tert-butyldimethylsilyl ether, reduction of the DELTA24(28) bond with hydrogen over platinum oxide, and deprotection gave principally (20R,23R,24R)-5alpha-dinosteran-29-ol. The further reduction of this alcohol provided (20R,23R,24R)-5alpha-dinosterane (2b). The application of the same sequence of reactions to (20R,23S)-5alpha-dinoster-24(28)-en-29-ol provided (20R,23S,24S)-5alpha-dinosterane (2c). Diastereoselectivity at the C-23 position in these ester alkylations was examined as a function of stereochemistry at both the C-20 and C-24 positions.
• A synthesis of C-23 and C-24 diastereomers of 5α-dinosterane
  作者：Ivan Stoilov、Ewa Kolaczkowska、Jan St. Pyrek、Carolyn P. Brock、David S. Watt、R.M.K. Carlson、J.Michael Moldowan

  DOI：10.1016/0040-4039(93)88018-e

  日期：1992.12

  Stereoselective routes for the preparation of C-23 and C-24 diastereomers of the C30 biological marker, 5α-dinosterane (1), involved the alkylation of (20S)-20-(iodomethyl)-4α-methyl-5α-pregnane (7) with either a saturated ester, methyl 3,4-dimethylpentanoate (9), followed by reduction to give principally the erythro-diastereomers or the alkylation of 7 with an α,β-unsaturated ester, methyl 3,4-dimethylpentenoate

  制备C 30生物标记物5α-地甾烷（1）的C-23和C-24非对映异构体的立体选择路线涉及（20S）-20-（碘甲基）-4α-甲基-5α-孕烯（7）与3,4-二甲基戊酸甲酯饱和酯（9）结合，然后还原，主要得到赤型-非对映异构体或7，与α，β-不饱和酯3,4-二甲基戊烯酸甲酯烷基化（12）），然后还原，主要得到苏-非对映异构体。