4-methyl-4-azapregna-16,20-dien-3-one | 172301-21-2

• 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: 4-methyl-4-azapregna-16,20-dien-3-one
• 英文别名: (3aS,3bS,9aR,9bS,11aS)-1-ethenyl-6,9a,11a-trimethyl-3a,3b,4,5,5a,8,9,9b,10,11-decahydro-3H-indeno[5,4-f]quinolin-7-one
• CAS: 172301-21-2
• 化学式: C₂₁H₃₁NO
• 分子量: 313.483
• InChiKey: OOPFNXUREYDYFY-SKIHVZLESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  23
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  马来酸酐 、 4-methyl-4-azapregna-16,20-dien-3-one 以 甲苯 为溶剂， 以96%的产率得到1'α,2'α-(oxydicarbonyl-3-keto-4-methyl-4-azaandrostano)[16α,17-c]cyclohex-4'-ene
  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-iodo-4-aza-4-methylandrost-16-en-3-one 在 四(三苯基膦)钯 作用下， 以 甲苯 为溶剂， 生成 4-methyl-4-azapregna-16,20-dien-3-one
  参考文献：
  名称：

  Cycloaddition of Nitrosoaromatics with Steroidal Dienes:  Unexpected Dependence of the Chemoselectivity on the Aryl Ring Substituent

  摘要：

  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.

  DOI：

  10.1021/jo9904157

文献信息

• Palladium-catalyzed homogeneous coupling reactions of steroids with organostannanes
  作者：Rita Skoda-Földes、Zita Csákai、Lászlo Kollár、Judit Horváth、Zoltán Tuba

  DOI：10.1016/0039-128x(95)00146-h

  日期：1995.12

  Direct and carbonylative coupling reactions of various steroid derivatives possessing iodo- and bromo-alkenyl moiety (17-iodo-androst-16-ene, 1, 17-bromoandrost-2, 16-diene, 2, 17-iodo-4-aza-4-methylandrost-16-en-3-one, 3, 17-iodo-4-azaandrost-16-en-3-one, 4) with vinyltributylstannane and ethynyltributylstannane were carried out in the presence of various palladium catalysts. While carbonylation took place only with vinyltributylstannane, 17-vinyl-, and 17-ethynyl-Delta(16) steroids were produced via direct coupling with vinyltributylstannane and ethynyltributylstannane, respectively. Activities of some catalysts based on Pd(0) and Pd(II) precursors were compared, and Pd(PPh(3))(4) was found to be superior to other complexes in most cases. In the coupling of 17-iodoandrost-16-ene with organostannanes Pd-2(dba)(3) + 8 AsPh(3) in situ catalyst was found to be even more effective.