(3S,4R,5R)-5-benzyloxymethyl-1-(tert-butoxycarbonyl)-3,4-dibenzyloxy-pyrrolidin-2-one | 944544-00-7

• 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: (3S,4R,5R)-5-benzyloxymethyl-1-(tert-butoxycarbonyl)-3,4-dibenzyloxy-pyrrolidin-2-one
• 英文别名: tert-butyl (3S,4R,5R)-2-oxo-3,4-bis(phenylmethoxy)-5-(phenylmethoxymethyl)pyrrolidine-1-carboxylate
• CAS: 944544-00-7
• 化学式: C₃₁H₃₅NO₆
• 分子量: 517.622
• InChiKey: NQBGXQWPWUHEOE-FCEKVYKBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  38
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  74.3
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (3S,4R,5R)-5-benzyloxymethyl-1-(tert-butoxycarbonyl)-3,4-dibenzyloxy-pyrrolidin-2-one 在 三乙基硅烷 、 三氟化硼乙醚 、 potassium carbonate 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 反应 26.0h， 生成 (2R,3R,4R,5S)-1-benzyl-2-benzyloxymethyl-3,4-dibenzyloxy-5-methylpyrrolidine
  参考文献：
  名称：

  A versatile approach to pyrrolidine azasugars and homoazasugars based on a highly diastereoselective reductive benzyloxymethylation of protected tartarimide

  摘要：

  A highly diastereoselective synthesis of enantio-enriched all trans-3,4-dibenzyloxyl-5-benzyloxymethyl-2-pyrrolidinone 13a was developed based on SmI2-mediated benzyloxymethylation of O,O'-dibenzyltartarimide. The versatility of 13a and its antipode as the key building blocks for the asymmetric synthesis of pyrrolidine azasugars and homoazasugars has been demonstrated by elaborating them into naturally occurring DAB 1 (1), LAB 1 (2), N-hydroxyethyl-DAB 1 (4), 6-deoxy-DMDP 7, and 5-epi-radicamine B 36 as well as the reductive ring-opening product 35. (c) 2007 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tet.2007.02.087
• 作为产物：
  描述：

  L-O,O-dibenzyltartaric acid 在 三乙基硅烷 、 4-二甲氨基吡啶 、 ammonium cerium(IV) nitrate 、 三氟化硼乙醚 、 magnesium 、 三乙胺 、 乙酰氯 、 mercury dichloride 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 31.5h， 生成 (3S,4R,5R)-5-benzyloxymethyl-1-(tert-butoxycarbonyl)-3,4-dibenzyloxy-pyrrolidin-2-one
  参考文献：
  名称：

  A versatile approach to pyrrolidine azasugars and homoazasugars based on a highly diastereoselective reductive benzyloxymethylation of protected tartarimide

  摘要：

  A highly diastereoselective synthesis of enantio-enriched all trans-3,4-dibenzyloxyl-5-benzyloxymethyl-2-pyrrolidinone 13a was developed based on SmI2-mediated benzyloxymethylation of O,O'-dibenzyltartarimide. The versatility of 13a and its antipode as the key building blocks for the asymmetric synthesis of pyrrolidine azasugars and homoazasugars has been demonstrated by elaborating them into naturally occurring DAB 1 (1), LAB 1 (2), N-hydroxyethyl-DAB 1 (4), 6-deoxy-DMDP 7, and 5-epi-radicamine B 36 as well as the reductive ring-opening product 35. (c) 2007 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tet.2007.02.087

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.
• A versatile approach to pyrrolidine azasugars and homoazasugars based on a highly diastereoselective reductive benzyloxymethylation of protected tartarimide
  作者：Xiang Zhou、Wen-Jun Liu、Jian-Liang Ye、Pei-Qiang Huang

  DOI：10.1016/j.tet.2007.02.087

  日期：2007.7

  A highly diastereoselective synthesis of enantio-enriched all trans-3,4-dibenzyloxyl-5-benzyloxymethyl-2-pyrrolidinone 13a was developed based on SmI2-mediated benzyloxymethylation of O,O'-dibenzyltartarimide. The versatility of 13a and its antipode as the key building blocks for the asymmetric synthesis of pyrrolidine azasugars and homoazasugars has been demonstrated by elaborating them into naturally occurring DAB 1 (1), LAB 1 (2), N-hydroxyethyl-DAB 1 (4), 6-deoxy-DMDP 7, and 5-epi-radicamine B 36 as well as the reductive ring-opening product 35. (c) 2007 Published by Elsevier Ltd.