(2R,3S)-3-(tert-butyldimethylsilyloxy)-1-(tert-butyloxycarbonyl)-2-(pyridin-2-ylthio)pyrrolidine | 847942-46-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (2R,3S)-3-(tert-butyldimethylsilyloxy)-1-(tert-butyloxycarbonyl)-2-(pyridin-2-ylthio)pyrrolidine
• 英文别名: tert-butyl (2R,3S)-3-[tert-butyl(dimethyl)silyl]oxy-2-pyridin-2-ylsulfanylpyrrolidine-1-carboxylate
• CAS: 847942-46-5
• 化学式: C₂₀H₃₄N₂O₃SSi
• 分子量: 410.653
• InChiKey: WOTMLJNBGXBJHX-DOTOQJQBSA-N

物化性质

• 沸点：
  466.0±45.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.53
• 重原子数：
  27
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  77
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2R,3S)-3-(tert-butyldimethylsilyloxy)-1-(tert-butyloxycarbonyl)-2-(pyridin-2-ylthio)pyrrolidine 在 甲醇 、 samarium diiodide 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以95%的产率得到(S)-3-(tert-butyldimethylsilyloxy)-1-(tert-butyloxycarbonyl)pyrrolidine
  参考文献：
  名称：

  Samarium Diiodide Promoted Generation and Asymmetric Hydroxyalkylation of N,O-Diprotected (3S)-3-Pyrrolidinol 2-Carbanions

  摘要：

  The N,O-diprotected chiral nonracemic 2-pyridyl 3-pyrrolidinol-2-yl sulfide 5a undergoes efficient SMl(2) mediated reduction to give the N,O-diprotected 3-pyrrolidinol 2-carbanion intermediate D, which reacted under Barbier-type conditions with ketones and alclehydes to afford the protected N-alpha-hydroxyalkyl-3-pyrrolidines 10b-h with excellent diastereoselectivity at the newly formed chiral center in the pyrrolidine ring. Application of the present method led to the formal asymmetric syntheses of (2R,3S)-2-hydroxymethyl-3-pyrrolidinol (2) and (2S,3S)-3hydroxyproline (12).

  DOI：

  10.1021/ol047733z
• 作为产物：
  描述：

  (S)-3-((tert-butyldimethylsilyl)oxy)pyrrolidin-2-one 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 4-甲基苯磺酸吡啶 、 对甲苯磺酸 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 48.33h， 生成 (2R,3S)-3-(tert-butyldimethylsilyloxy)-1-(tert-butyloxycarbonyl)-2-(pyridin-2-ylthio)pyrrolidine
  参考文献：
  名称：

  Samarium Diiodide Promoted Generation and Asymmetric Hydroxyalkylation of N,O-Diprotected (3S)-3-Pyrrolidinol 2-Carbanions

  摘要：

  The N,O-diprotected chiral nonracemic 2-pyridyl 3-pyrrolidinol-2-yl sulfide 5a undergoes efficient SMl(2) mediated reduction to give the N,O-diprotected 3-pyrrolidinol 2-carbanion intermediate D, which reacted under Barbier-type conditions with ketones and alclehydes to afford the protected N-alpha-hydroxyalkyl-3-pyrrolidines 10b-h with excellent diastereoselectivity at the newly formed chiral center in the pyrrolidine ring. Application of the present method led to the formal asymmetric syntheses of (2R,3S)-2-hydroxymethyl-3-pyrrolidinol (2) and (2S,3S)-3hydroxyproline (12).

  DOI：

  10.1021/ol047733z

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.
• Samarium Diiodide Promoted Generation and Asymmetric Hydroxyalkylation of <i>N</i>,<i>O-</i>Diprotected (3<i>S</i>)-3-Pyrrolidinol 2-Carbanions
  作者：Xiao Zheng、Chen-Guo Feng、Jian-Liang Ye、Pei-Qiang Huang

  DOI：10.1021/ol047733z

  日期：2005.2.1

  The N,O-diprotected chiral nonracemic 2-pyridyl 3-pyrrolidinol-2-yl sulfide 5a undergoes efficient SMl(2) mediated reduction to give the N,O-diprotected 3-pyrrolidinol 2-carbanion intermediate D, which reacted under Barbier-type conditions with ketones and alclehydes to afford the protected N-alpha-hydroxyalkyl-3-pyrrolidines 10b-h with excellent diastereoselectivity at the newly formed chiral center in the pyrrolidine ring. Application of the present method led to the formal asymmetric syntheses of (2R,3S)-2-hydroxymethyl-3-pyrrolidinol (2) and (2S,3S)-3hydroxyproline (12).