17-iodo-4-aza-4-methylandrost-16-en-3-one | 204317-14-6

• 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: 17-iodo-4-aza-4-methylandrost-16-en-3-one
• 英文别名: (3aS,3bR,9aR,9bS,11aS)-1-iodo-6,9a,11a-trimethyl-3a,3b,4,5,5a,8,9,9b,10,11-decahydro-3H-indeno[5,4-f]quinolin-7-one
• CAS: 204317-14-6
• 化学式: C₁₉H₂₈INO
• 分子量: 413.342
• InChiKey: WNESZHJHOJBPGS-SWXBFBGGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.84
• 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：

  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 (2'-(4"-nitro)-phenyl)-(3-keto-4-methyl-4-aza-androstano)-[16,17-e]-3',6'-dihydro-1',2'-oxazine
  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
• 作为产物：
  描述：

  亚磷酸二甲酯 、 17-iodo-4-aza-androst-16-en-3-one 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 三乙胺 作用下， 反应 5.0h， 生成 17-iodo-4-aza-4-methylandrost-16-en-3-one 、 dimethyl 4-aza-androst-16-en-3-one-17-phosphonate 、 dimethyl 4-methyl-4-aza-androst-16-en-3-one-17-phosphonate
  参考文献：
  名称：

  Steroidal alkenylphosphonates via palladium-catalyzed coupling reactions

  摘要：

  The palladium-catalyzed coupling of various 17-iodo-Delta(16) steroids (17-iodo-androst-16-ene, 17-iodo-4-methyl-4-aza-androst-16-en-3-one, and 17-iodo-4-aza-androst-16-en-3-one) with dialkyl phosphites (dimethyl phosphite, diethyl phosphite, and diisopropyl phosphite) was examined in detail. The only successful condition for homogeneous coupling involved carrying out the reaction in the absence of any solvents. A large excess of dialkyl phosphite was used, which means that the phosphite itself acted as a solvent. Eight new androst-16-ene derivatives with phosphonate groups at C-17 were synthesized and characterized. These steroids are of pharmacological interest as potential Sol-reductase inhibitors. Under the same conditions, methylation of lactam NH was observed using dimethyl phosphite.

  DOI：

  10.1016/0039-128x(95)00121-6

文献信息

• Synthesis of new steroid-β-lactam hybrids via palladium-catalyzed aminocarbonylation
  作者：János Balogh、Rita Skoda-Földes、Katarina Vazdar、Ivan Habuš

  DOI：10.1016/j.jorganchem.2011.12.033

  日期：2012.4

  Steroid-β-lactam and steroid-β-lactam-ferrocene conjugates were synthesized via palladium-catalyzed carbonylation of steroidal 17-iodo-16-enes in the presence of 3-amino-azetidin-2-ones. β-Lactam derivatives have been used for the first time as nucleophiles in the aminocarbonylation reaction. The products were obtained in good yields and were characterized by 1H and 13C NMR, IR and HRMS.

  在3-氨基氮杂环丁烷-2-酮的存在下，通过钯催化的甾族17-碘-16-烯的羰基化反应合成了甾体-β-内酰胺和甾体-β-内酰胺-二茂铁共轭物。β-内酰胺衍生物首次在氨基羰基化反应中用作亲核试剂。以高收率获得产物，并通过1 H和13 C NMR，IR和HRMS进行表征。
• Highly Efficient Synthesis of Steroidal Hydroxamic Acid Derivatives via Homogeneous Catalytic Carbonylation Reaction
  作者：Zsolt Szarka、Rita Skoda-Földes、László Kollár、Zoltán Berente、Judit Horváth、Zoltán Tuba

  DOI：10.1016/s0040-4020(00)00435-x

  日期：2000.7

  Steroidal hydroxamic acid derivatives were synthesized in moderate to high yields by palladium-catalyzed carbonylation reactions of the corresponding iodo-alkenyl compounds or enol triflates in the presence of substituted hydroxylamines under mild reaction conditions. The effect of reaction parameters on the regioselectivity of carbonylation of N-substituted hydroxylamines is investigated in detail

  在适当的反应条件下，在取代的羟胺存在下，相应的碘-烯基化合物或烯醇三氟甲磺酸酯经钯催化的羰基化反应，以中等至高收率合成了甾体异羟肟酸衍生物。详细研究了反应参数对N-取代羟胺羰基化区域选择性的影响。
• The synthesis of pentacyclic steroidal polyesters in consecutive Heck- and Diels-Alder reactions
  作者：György Jeges、Rita Skoda-Földes、László Kollár、Judit Horváth、Zoltán Tuba

  DOI：10.1016/s0040-4020(98)00361-5

  日期：1998.6

  Steroidal alkenyl iodides (17-iodo-androsta-16-ene and 17-iodo-4-methyl-4-aza-androsta-16-ene-3-one) were reacted with conjugated unsaturated esters (ethyl acrylate, diethyl fumarate, diethyl maleate, diethyl acetylene dicarboxylate) in Heck-reaction and consecutive Diels-Alder reaction resulting in facile formation of pentacyclic derivatives. All steroidal esters possessing two, three and four ester

  使类固醇链烯基碘化物（17-碘-androsta-16-ene和17-io-4--4-甲基-4-aza-androsta-16-ene-3-one）与共轭不饱和酯（丙烯酸乙酯，富马酸二乙酯，二乙酯）反应马来酸酯，乙炔二甲酸二乙酯）在Heck反应和连续的Diels-Alder反应中导致五环衍生物的容易形成。所有在E环上具有两个，三个和四个酯官能度的甾体酯都是通过添加亲二烯体的α侧形成的。
• Synthesis of N-Substituted Steroidal Hydrazides in Homogeneous Catalytic Hydrazinocarbonylation Reaction
  作者：Rita Skoda-Földes、Zsolt Szarka、László Kollár、Zoltán Dinya、Judit Horváth、Zoltán Tuba

  DOI：10.1021/jo9819842

  日期：1999.3.1
• Synthesis of Pentacyclic Steroids via Tandem Stille Coupling and Diels−Alder Reactions
  作者：Rita Skoda-Földes、György Jeges、László Kollár、Judit Horváth、Zoltán Tuba

  DOI：10.1021/jo9615256

  日期：1997.3.1

  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.