(20S)-20-(Hydroxymethyl)-4-methyl-19-norpregna-1,3,5(10)-triene | 161007-13-2

• 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: (20S)-20-(Hydroxymethyl)-4-methyl-19-norpregna-1,3,5(10)-triene
• 英文别名: (2S)-2-[(8S,9S,13S,14S,17R)-4,13-dimethyl-6,7,8,9,11,12,14,15,16,17-decahydrocyclopenta[a]phenanthren-17-yl]propan-1-ol
• CAS: 161007-13-2
• 化学式: C₂₂H₃₂O
• 分子量: 312.495
• InChiKey: FQMIOWZPDTZPRW-KCRXAXGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (20S)-20-(Hydroxymethyl)-4-methyl-19-norpregna-1,3,5(10)-triene 在 lithium aluminium tetrahydride 、 三乙胺 、 sodium iodide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 二氯甲烷 、 丙酮 为溶剂， 反应 18.67h， 生成 (20R,23S,24R)-4,23,24-Trimethyl-19-norcholesta-1,3,5(10)-triene
  参考文献：
  名称：

  Synthesis of Biomarkers in Fossil Fuels: C-23 and C-24 Diastereomers of (20R)-4,17.beta.,23,24-Tetramethyl-18,19-dinorcholesta-1,3,5,7,9,11,13-heptaene

  摘要：

  A synthesis of the C-23 and C-24 diastereomers of triaromatic dinosteroids useful as maturation biomarkers for marine-sourced petroleum was developed. Conversion of stigmasterol to (20R,22E,24S)-4-methyl-19-norstigmasta-1,3,5(10),22-tetraene, ozonolysis of the stigmasterol sidechain, sodium borohydride reduction, and sequential treatment with methanesulfonyl chloride and sodium iodide furnished (20S)-20-(iodomethyl)-4-methyl-19-norpregna-1,3,5(10)-triene. The alkylation of this iodide with methyl 3,4-dimethyl-2-pentenoate provided the C-23R and C-23S diastereomers of methyl (20R,23 xi)-4-methyl-24-methylene-19-norcholesta-1,3,5(10)-triene-23-carboxylate, reduction with lithium aluminum hydride, and separation gave (20R,23R)- and (20R,23S)-23-(hydroxymethyl)-4-methyl-24-methylene-19-norcholesta-1,3 The further reduction of the 24-methylene and the hydroxymethyl group in (20R,23R)-23-(hydroxymethyl)-4-methyl-24-methyl-19-norcholesta-1,3,5(10)-triene provided (20R,23R,24R)- and (20R,23R,24S)-4,23,24-trimethyl-19-norcholesta-1,3,5(10)-triene. In the same fashion, the reduction of the 24-methylene and the hydroxymethyl group in (20R,23S)-23-(hydroxymethyl)-4-methyl-24-methylene-19-norcholesta-1,3, 5(10)-triene provided (20R,23S,24R)- and (20R,23S,24S)-4,23,24-trimethyl-19-norcholesta-1,3,5-(10)-triene. A chloranil oxidation of each of these monoaromatic diastereomers to (20R)-4,17 beta,23,24-tetramethyl-18,19-dinorcholesta-1,3,5,7,9,11,13,15-octaene and a catalytic hydrogenation furnished the C-23 and C-24 diastereomers of the triaromatic biomarker, (20R)-4,17 beta,23,24-tetramethyl-18,19-dinorcholesta-1,3,5,7,9,11,13-heptaene.

  DOI：

  10.1021/jo00105a043
• 作为产物：
  描述：

  (20R,22E,24S)-4-Methylstigmasta-1,3,5(10),22-tetraene 在 sodium tetrahydroborate 、 二甲基硫 、 臭氧 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 1.75h， 生成 (20S)-20-(Hydroxymethyl)-4-methyl-19-norpregna-1,3,5(10)-triene
  参考文献：
  名称：

  Synthesis of Biomarkers in Fossil Fuels: C-23 and C-24 Diastereomers of (20R)-4,17.beta.,23,24-Tetramethyl-18,19-dinorcholesta-1,3,5,7,9,11,13-heptaene

  摘要：

  A synthesis of the C-23 and C-24 diastereomers of triaromatic dinosteroids useful as maturation biomarkers for marine-sourced petroleum was developed. Conversion of stigmasterol to (20R,22E,24S)-4-methyl-19-norstigmasta-1,3,5(10),22-tetraene, ozonolysis of the stigmasterol sidechain, sodium borohydride reduction, and sequential treatment with methanesulfonyl chloride and sodium iodide furnished (20S)-20-(iodomethyl)-4-methyl-19-norpregna-1,3,5(10)-triene. The alkylation of this iodide with methyl 3,4-dimethyl-2-pentenoate provided the C-23R and C-23S diastereomers of methyl (20R,23 xi)-4-methyl-24-methylene-19-norcholesta-1,3,5(10)-triene-23-carboxylate, reduction with lithium aluminum hydride, and separation gave (20R,23R)- and (20R,23S)-23-(hydroxymethyl)-4-methyl-24-methylene-19-norcholesta-1,3 The further reduction of the 24-methylene and the hydroxymethyl group in (20R,23R)-23-(hydroxymethyl)-4-methyl-24-methyl-19-norcholesta-1,3,5(10)-triene provided (20R,23R,24R)- and (20R,23R,24S)-4,23,24-trimethyl-19-norcholesta-1,3,5(10)-triene. In the same fashion, the reduction of the 24-methylene and the hydroxymethyl group in (20R,23S)-23-(hydroxymethyl)-4-methyl-24-methylene-19-norcholesta-1,3, 5(10)-triene provided (20R,23S,24R)- and (20R,23S,24S)-4,23,24-trimethyl-19-norcholesta-1,3,5-(10)-triene. A chloranil oxidation of each of these monoaromatic diastereomers to (20R)-4,17 beta,23,24-tetramethyl-18,19-dinorcholesta-1,3,5,7,9,11,13,15-octaene and a catalytic hydrogenation furnished the C-23 and C-24 diastereomers of the triaromatic biomarker, (20R)-4,17 beta,23,24-tetramethyl-18,19-dinorcholesta-1,3,5,7,9,11,13-heptaene.

  DOI：

  10.1021/jo00105a043

文献信息

• Synthesis of Biomarkers in Fossil Fuels: C-23 and C-24 Diastereomers of (20R)-4,17.beta.,23,24-Tetramethyl-18,19-dinorcholesta-1,3,5,7,9,11,13-heptaene
  作者：Rupa Shetty、Ivan Stoilov、David S. Watt、R. M. K. Carlson、Frederick J. Fago、J. Michael Moldowan

  DOI：10.1021/jo00105a043

  日期：1994.12

  A synthesis of the C-23 and C-24 diastereomers of triaromatic dinosteroids useful as maturation biomarkers for marine-sourced petroleum was developed. Conversion of stigmasterol to (20R,22E,24S)-4-methyl-19-norstigmasta-1,3,5(10),22-tetraene, ozonolysis of the stigmasterol sidechain, sodium borohydride reduction, and sequential treatment with methanesulfonyl chloride and sodium iodide furnished (20S)-20-(iodomethyl)-4-methyl-19-norpregna-1,3,5(10)-triene. The alkylation of this iodide with methyl 3,4-dimethyl-2-pentenoate provided the C-23R and C-23S diastereomers of methyl (20R,23 xi)-4-methyl-24-methylene-19-norcholesta-1,3,5(10)-triene-23-carboxylate, reduction with lithium aluminum hydride, and separation gave (20R,23R)- and (20R,23S)-23-(hydroxymethyl)-4-methyl-24-methylene-19-norcholesta-1,3 The further reduction of the 24-methylene and the hydroxymethyl group in (20R,23R)-23-(hydroxymethyl)-4-methyl-24-methyl-19-norcholesta-1,3,5(10)-triene provided (20R,23R,24R)- and (20R,23R,24S)-4,23,24-trimethyl-19-norcholesta-1,3,5(10)-triene. In the same fashion, the reduction of the 24-methylene and the hydroxymethyl group in (20R,23S)-23-(hydroxymethyl)-4-methyl-24-methylene-19-norcholesta-1,3, 5(10)-triene provided (20R,23S,24R)- and (20R,23S,24S)-4,23,24-trimethyl-19-norcholesta-1,3,5-(10)-triene. A chloranil oxidation of each of these monoaromatic diastereomers to (20R)-4,17 beta,23,24-tetramethyl-18,19-dinorcholesta-1,3,5,7,9,11,13,15-octaene and a catalytic hydrogenation furnished the C-23 and C-24 diastereomers of the triaromatic biomarker, (20R)-4,17 beta,23,24-tetramethyl-18,19-dinorcholesta-1,3,5,7,9,11,13-heptaene.