tert-butyl (3S,4R,5R)-2-hydroxy-3,4-bis(phenylmethoxy)-5-(phenylmethoxymethyl)pyrrolidine-1-carboxylate | 1329714-94-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: tert-butyl (3S,4R,5R)-2-hydroxy-3,4-bis(phenylmethoxy)-5-(phenylmethoxymethyl)pyrrolidine-1-carboxylate
• CAS: 1329714-94-4
• 化学式: C₃₁H₃₇NO₆
• 分子量: 519.638
• InChiKey: AVKBZATVWPBLPY-HFVNIMEJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  38
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  77.5
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  tert-butyl (3S,4R,5R)-2-hydroxy-3,4-bis(phenylmethoxy)-5-(phenylmethoxymethyl)pyrrolidine-1-carboxylate 在 盐酸 、 samarium diiodide 、 三氟化硼乙醚 、 calcium chloride 、 叔丁醇 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 乙酸乙酯 为溶剂， 反应 48.5h， 生成 (5R,6R,7R,7aR)-6,7-bis-benzyloxy-5-benzyloxymethylhexahydropyrrolizin-3-one
  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
• 作为产物：
  描述：

  (3S,4R,5R)-5-benzyloxymethyl-1-(tert-butoxycarbonyl)-3,4-dibenzyloxy-pyrrolidin-2-one 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 1.0h， 生成 tert-butyl (3S,4R,5R)-2-hydroxy-3,4-bis(phenylmethoxy)-5-(phenylmethoxymethyl)pyrrolidine-1-carboxylate
  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.