(2S,3S)-3-tert-butyldimethylsilyloxy-1-tert-butyloxycarbonyl-2-(2-cyanoethyl)piperidine | 1310339-86-6

• 分子结构分类: 有机化合物 - 生物碱及其衍生物
• 英文名称: (2S,3S)-3-tert-butyldimethylsilyloxy-1-tert-butyloxycarbonyl-2-(2-cyanoethyl)piperidine
• 英文别名: tert-butyl (2S,3S)-3-[tert-butyl(dimethyl)silyl]oxy-2-(2-cyanoethyl)piperidine-1-carboxylate
• CAS: 1310339-86-6
• 化学式: C₁₉H₃₆N₂O₃Si
• 分子量: 368.592
• InChiKey: GZCAAPXPFKUWKV-HOTGVXAUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.08
• 重原子数：
  25
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  62.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  tert-butyl (S)-3-((tert-butyldimethylsilyl)oxy)-2-oxopiperidine-1-carboxylate 在 samarium diiodide 、 三氟化硼乙醚 、 二异丁基氢化铝 、 叔丁醇 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 1.17h， 生成 (2S,3S)-3-tert-butyldimethylsilyloxy-1-tert-butyloxycarbonyl-2-(2-cyanoethyl)piperidine 、 (2R,3S)-3-tert-butyldimethylsilyloxy-1-tert-butyloxycarbonyl-2-(2-cyanoethyl)piperidine
  参考文献：
  名称：

  SmI₂-Mediated Radical Cross-Couplings of α-Hydroxylated Aza-hemiacetals andN,S-Acetals with α,β-Unsaturated Compounds: Asymmetric Synthesis of (+)-Hyacinthacine A₂, (−)-Uniflorine A, and (+)-7-epi-Casuarine

  摘要：

  The SmI2-mediated radical coupling reactions of beta-hydroxylated pyrrolidine/piperidine aza-hemiacetals 8 and 9 and N,S-acetals 6 and 33 with alpha/beta-unsaturated compounds are described. This method allows a rapid access to beta-hydroxylated pyrrolidines, piperidines, pyrrolizidinones, and indolizidinones. Starting from N,S-acetal 33 and via a common intermediate 27, the alkaloids hyacinthacine A(2) (2), uniflorine A (3, 6-epi-casuarine), and the unnatural epimer 7-epi-casuarine (37) have been synthesized in four and five steps with overall yields of 34%, 16%, and 13%, respectively. The radical mechanism of the coupling reactions has been confirmed by controlled experiments, which also allowed deducing the anionic mechanism in the coupling between N,S-acetal 6 and carbonyl compounds. This demonstrates that the mechanisms of these SmI2-mediated reactions are switchable from Barbier-type anionic to radical by cooperative action of BF3 center dot OEt2 and t-BuOH.

  DOI：

  10.1021/jo200600n

文献信息

• SmI₂-Mediated Radical Cross-Couplings of α-Hydroxylated Aza-hemiacetals and<i>N</i>,<i>S</i>-Acetals with α,β-Unsaturated Compounds: Asymmetric Synthesis of (+)-Hyacinthacine A₂, (−)-Uniflorine A, and (+)-7-<i>epi</i>-Casuarine
  作者：Xue-Kui Liu、Shi Qiu、Yong-Gang Xiang、Yuan-Ping Ruan、Xiao Zheng、Pei-Qiang Huang

  DOI：10.1021/jo200600n

  日期：2011.6.17

  The SmI2-mediated radical coupling reactions of beta-hydroxylated pyrrolidine/piperidine aza-hemiacetals 8 and 9 and N,S-acetals 6 and 33 with alpha/beta-unsaturated compounds are described. This method allows a rapid access to beta-hydroxylated pyrrolidines, piperidines, pyrrolizidinones, and indolizidinones. Starting from N,S-acetal 33 and via a common intermediate 27, the alkaloids hyacinthacine A(2) (2), uniflorine A (3, 6-epi-casuarine), and the unnatural epimer 7-epi-casuarine (37) have been synthesized in four and five steps with overall yields of 34%, 16%, and 13%, respectively. The radical mechanism of the coupling reactions has been confirmed by controlled experiments, which also allowed deducing the anionic mechanism in the coupling between N,S-acetal 6 and carbonyl compounds. This demonstrates that the mechanisms of these SmI2-mediated reactions are switchable from Barbier-type anionic to radical by cooperative action of BF3 center dot OEt2 and t-BuOH.