3β-hydroxy-12-iodo-5α,25R-spirost-11-ene | 944938-27-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 3β-hydroxy-12-iodo-5α,25R-spirost-11-ene
• 英文别名: 12-iodo-3β-hydroxyspirost-11-ene；(1S,2S,4S,5'R,6R,7S,8R,9S,12R,13S,16S,18S)-10-iodo-5',7,9,13-tetramethylspiro[5-oxapentacyclo[10.8.0.02,9.04,8.013,18]icos-10-ene-6,2'-oxane]-16-ol
• CAS: 944938-27-6
• 化学式: C₂₇H₄₁IO₃
• 分子量: 540.525
• InChiKey: VIIMUTCGDULYOX-LOBDNJQFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  31
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3β-hydroxy-12-iodo-5α,25R-spirost-11-ene 、 一氧化碳 在 palladium diacetate 、 三乙胺 、 三苯基膦 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 50.0 ℃ 、100.0 kPa 条件下， 反应 6.0h， 以44%的产率得到3β-hydroxy-12-carboxyl-5α,25R-spirost-11-ene
  参考文献：
  名称：

  Facile synthesis of 12-carboxamido-11-spirostenes via palladium-catalyzed carbonylation reactions

  摘要：

  12-Carboxamido- and 12-carboxyl-11-spirostenes were synthesized from the corresponding 12-iodo-11-ene derivative in palladium-catalyzed carbonylation reactions under mild reaction conditions. The synthesis of the iodo-alkene substrate is based on the transformation of the 12-keto derivative (hecogenin) to hydrazone, which was treated with iodine in the presence of a base (1,1,3,3-tetramethyl guanidine). While various 12-carboxamides were synthesized in moderate to high yields by using simple alky/arylamines or amino acid methylesters as N-nucleophiles, low yields can be achieved with alcohols as O-nucleophiles. The homogeneous carbonylation reactions tolerate the 3-hydroxy substituent and the spiroacetal moiety. (c) 2006 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.steroids.2006.05.019
• 作为产物：
  描述：

  海柯吉宁 在 碘 、 肼 作用下， 生成 3β-hydroxy-12-iodo-5α,25R-spirost-11-ene
  参考文献：
  名称：

  氨基羰基化反应合成N-吡啶甲基羧酰胺

  摘要：

  在2-，3-和4-吡啶甲基胺以及具有1-吡啶甲基取代基的仲胺存在下，进行钯催化的碘樟脑和甾体碘代烯烃的氨基羰基化。通常，伯甲基吡啶胺需要少于2小时才能实现几乎完全的转化。仲胺被证明反应性较低，需要6-24小时，具体取决于底物结构。分离出相应的羧酰胺，产率中等至优异。α，β-不饱和羧酰​​胺的合成是基于由可烯醇化的酮合成碘代烯烃底物。

  DOI：

  10.1016/j.tet.2021.132128

文献信息

• Asymmetric aminocarbonylation of iodoalkenes in the presence of α-phenylethylamine as an N -nucleophile
  作者：Gábor Mikle、Borbála Boros、László Kollár

  DOI：10.1016/j.tetasy.2017.10.012

  日期：2017.12

  lodoalkenes, such as 2-iodo-bornene, 17-iodoandrost-16-ene, 3-methoxy-17-iodoestra-1,3,5(10),16-ene, 3 beta-hydroxy-20-iodopregna-5,20-diene and 3 beta-hydroxy-12-iodo-5 alpha,25R-spirost-11-ene were aminocar-bonylated with enantiomerically pure and racemic alpha-phenylethylamine as the N-nucleophile in the presence of palladium(0) catalysts. Monodentate and bidentate (chiral and achiral) phosphines were used as ligands in the catalytic system. All diastereoisomers of the corresponding carboxamides were characterised as pure stereoisomers using both alpha-phenylethylamine and iodoalkene in enantiomerically pure form. The diastereoisomers were obtained in moderate to high yields in a chemoselective reaction, i.e., carboxamides due to single carbon monoxide insertion were formed exclusively, with no double CO insertion leading to 2-ketocarboxamides. Diastereoselectivities of the aminocarbonylation were investigated using the N-nucleophile in racemic form by the systematic variation of the catalyst. (C) 2017 Elsevier Ltd. All rights reserved.