17-ethenyl-androsta-16-ene | 136678-15-4

• 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: 17-ethenyl-androsta-16-ene
• 英文别名: pregna-16,20-diene；Pregnadiene；(8R,9S,10S,13S,14S)-17-ethenyl-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15-dodecahydro-1H-cyclopenta[a]phenanthrene
• CAS: 136678-15-4
• 化学式: C₂₁H₃₂
• 分子量: 284.485
• InChiKey: CPUKWYXYHPOQJH-RDQPJNLGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.4
• 重原子数：
  21
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  17-ethenyl-androsta-16-ene 、 富马酸二乙酯 以 甲苯 为溶剂， 以91%的产率得到diethyl (4aS,4bS,6aS,9S,10S,10aS,11aS,11bR)-4a,6a-dimethyl-2,3,4,4b,5,6,8,9,10,10a,11,11a,11b,12,13,13a-hexadecahydro-1H-indeno[2,1-a]phenanthrene-9,10-dicarboxylate
  参考文献：
  名称：

  Synthesis of Pentacyclic Steroids via Tandem Stille Coupling and Diels−Alder Reactions

  摘要：

  Tandem Stille coupling and Diels-Alder reaction of steroidal iodoalkenyl substrates [17-iodoandrosta-16-ene (2), 17-iodo-3-keto-4-methyl-4-azaandrosta-16-ene (10), and 17-iodo-3-keto-4-azaandrosta-16-ene (11)] were examined in the presence of vinyltributyltin, a dienophile (diethyl maleate, methyl acrylate, dimethyl acetylenedicarboxylate, diethyl fumarate, (-)-di[(LR)-menthyl] fumarate, maleic anhydride), and a palladium catalyst. The yields of novel pentacyclic steroids and the stereochemical outcome of the cycloaddition reaction were investigated under different reaction conditions. In some cases mixtures of isomers were formed, but with dimethyl acetylenedicarboxylate, diethyl fumarate, (-)-di[(1R)-menthyl] fumarate, and maleic anhydride the products could be produced in good yields with high stereoselectivity. The unequivocal assignment of stereoisomers was carried out by various NMR techniques including H-1-H-1 COSY and NOE experiments.

  DOI：

  10.1021/jo9615256
• 作为产物：
  描述：

  三丁基乙烯基锡 、 17-iodoandrost-16-ene 在 四(三苯基膦)钯 作用下， 以 甲苯 为溶剂， 反应 5.0h， 以98%的产率得到17-ethenyl-androsta-16-ene
  参考文献：
  名称：

  具有碘代烯烃部分的类固醇的均相偶联和羰基化反应。催化和机械方面

  摘要：

  Androstane衍生物的17-iodo-16-ene和6-iodo-5-ene官能团（17-iodo-4-aza-5α-androsta-16-en-3-one（1），6-iodo-17-甲氧羰基-4-氮杂-androsta-5,16-dien-3-one（2），6,17-二碘-4-氮杂-androsta-5,16-dien-3-one（3），17-碘- Androsta-16-ene（4），6-iodo-17-（N，N-五亚甲基-羧酰胺基）-4-aza-androst-5,16-dien-3-one（5））与乙烯基-三丁基锡反应斯蒂勒反应。但是，钯催化的羰基化选择性地在位置17发生。31观察到“碘-乙烯基”官能团向原位形成的Pd（0）-三苯基膦物种的氧化加成。P-NMR光谱。当6-碘-5-烯官能团（在环B中）连接到甾族底物中的内酰胺部分（环A）时，分别在氩气或一氧化碳下检测到了双核钯

  DOI：

  10.1016/s0022-328x(99)00224-7

文献信息

• Cycloaddition of Nitrosoaromatics with Steroidal Dienes:  Unexpected Dependence of the Chemoselectivity on the Aryl Ring Substituent
  作者：Rita Skoda-Földes、Katalin Vándor、László Kollár、Judit Horváth、Zoltán Tuba

  DOI：10.1021/jo9904157

  日期：1999.8.1

  Tandem palladium-catalyzed Stille coupling of steroidal alkenyl iodides (17-iodo-androst-16-ene (1), 17-iodo-4-methyl-4-aza-androst-16-en-3-one (4), and 17-iodo-4-aza-androst-16-en-3-one (5)) with vinyltributylstannane and hetero Diels-Alder reaction of the products using nitrosobenzene or some para-substituted nitrosoaromatics (p-NO2, p-Br, p-Me, p-OMe) as dienophiles were investigated. Cycloaddition was regioselective in each case, but two stereoisomers were obtained in a 2:1 ratio with unsubstituted pregnadienes as reaction partners. Stereoselectivity was improved by the use of Lewis acid catalysts. The similar reaction of substituted nitrosoaromatics with highly negative Hammett substituent-constants (p-OH, p-NMe2) resulted in the spontaneous dehydrogenation of the dihydro-oxazine, which was followed by the formation of rearrangement products. The assignment of stereoisomers was carried out by various NMR techniques including H-1-H-1 COSY and NOESY experiments.
• A possible way for the introduction of α- and β-formyl-ethyl-substituents into the steroid-skeleton via coupling and carbonylation reactions
  作者：Rita Skoda-Földes、László Kollár、Bálint Heil、György Gálik、Zoltán Tuba、Antonio Arcade

  DOI：10.1016/s0957-4166(00)86115-7

  日期：1991.1

  Cholesta-3,5-dien-3-yl triflate and androsta-16-en-17-yl iodide were vinylated with palladium and the olefins hydroformylated in the presence of rhodium and platinum catalysts.