(+)-(3R,4R)-1-tert-butoxycarbonyl-3,4-bis(phenylsulfanyl)pyrrolidine | 722545-09-7

• 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: (+)-(3R,4R)-1-tert-butoxycarbonyl-3,4-bis(phenylsulfanyl)pyrrolidine
• 英文别名: tert-butyl (3R,4R)-3,4-bis(phenylsulfanyl)pyrrolidine-1-carboxylate
• CAS: 722545-09-7
• 化学式: C₂₁H₂₅NO₂S₂
• 分子量: 387.567
• InChiKey: QSGSGHSGHKNFHT-RTBURBONSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  80.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (+)-(3R,4R)-1-tert-butoxycarbonyl-3,4-bis(phenylsulfanyl)pyrrolidine 在 三乙胺 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 22.0h， 生成 (+)-(3R,4R)-1-trityl-3,4-bis(phenylsulfanyl)pyrrolidine
  参考文献：
  名称：

  Chiral pyrrolidine thioethers: effective nitrogen–sulfur donating ligands in palladium-catalyzed asymmetric allylic alkylations

  摘要：

  Enantiomeric cyclic, five-melnbered alcohols and tic-diols were converted into the corresponding mono- and bis(aryl-sulfanyl) derivatives with complete inversion of configuration at one or both stereogenic centers. The thus obtained chiral thioethers were tested in the Pd-catalyzed allylic alkylation of dimethyl malonate with rac-1,3-diphenyl-2-propenyl acetate. The purely S,S-donating C-2-symmetric chiral ligands showed poor to moderate enantioselectivity (up to 42%), while 1-alkyl-3,4-bis(aryl-thio)pyrrolidines afforded much higher results, 81-89% ee. When chiral pyrrolidine mono-thioethers were applied the observed enantioselectivity improved further to 86-90% ee. These results suggest that the pyrrolidine thioethers served as the N(sp(3)),S-donating chiral ligands. Examination of molecular models showed that the sense of stereoinduction, namely (R)-product from with (3R)-1-benzyl-3-(arylthio)pyrrolidine is in agreement with the nucleophilic attack being directed at the allylic carbon located trans to the sulfur atom in the intermediate eta(3)-allylpalladiuln complex. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.03.015
• 作为产物：
  描述：

  N-BOC-(3S,4S)-二羟基-四氢吡咯 、 二苯二硫醚 在 三丁基膦 作用下， 以 苯 为溶剂， 反应 72.0h， 以79%的产率得到(+)-(3R,4R)-1-tert-butoxycarbonyl-3,4-bis(phenylsulfanyl)pyrrolidine
  参考文献：
  名称：

  Chiral pyrrolidine thioethers: effective nitrogen–sulfur donating ligands in palladium-catalyzed asymmetric allylic alkylations

  摘要：

  Enantiomeric cyclic, five-melnbered alcohols and tic-diols were converted into the corresponding mono- and bis(aryl-sulfanyl) derivatives with complete inversion of configuration at one or both stereogenic centers. The thus obtained chiral thioethers were tested in the Pd-catalyzed allylic alkylation of dimethyl malonate with rac-1,3-diphenyl-2-propenyl acetate. The purely S,S-donating C-2-symmetric chiral ligands showed poor to moderate enantioselectivity (up to 42%), while 1-alkyl-3,4-bis(aryl-thio)pyrrolidines afforded much higher results, 81-89% ee. When chiral pyrrolidine mono-thioethers were applied the observed enantioselectivity improved further to 86-90% ee. These results suggest that the pyrrolidine thioethers served as the N(sp(3)),S-donating chiral ligands. Examination of molecular models showed that the sense of stereoinduction, namely (R)-product from with (3R)-1-benzyl-3-(arylthio)pyrrolidine is in agreement with the nucleophilic attack being directed at the allylic carbon located trans to the sulfur atom in the intermediate eta(3)-allylpalladiuln complex. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.03.015

文献信息

• Chiral pyrrolidine thioethers: effective nitrogen–sulfur donating ligands in palladium-catalyzed asymmetric allylic alkylations
  作者：Renata Siedlecka、Elżbieta Wojaczyńska、Jacek Skarżewski

  DOI：10.1016/j.tetasy.2004.03.015

  日期：2004.5

  Enantiomeric cyclic, five-melnbered alcohols and tic-diols were converted into the corresponding mono- and bis(aryl-sulfanyl) derivatives with complete inversion of configuration at one or both stereogenic centers. The thus obtained chiral thioethers were tested in the Pd-catalyzed allylic alkylation of dimethyl malonate with rac-1,3-diphenyl-2-propenyl acetate. The purely S,S-donating C-2-symmetric chiral ligands showed poor to moderate enantioselectivity (up to 42%), while 1-alkyl-3,4-bis(aryl-thio)pyrrolidines afforded much higher results, 81-89% ee. When chiral pyrrolidine mono-thioethers were applied the observed enantioselectivity improved further to 86-90% ee. These results suggest that the pyrrolidine thioethers served as the N(sp(3)),S-donating chiral ligands. Examination of molecular models showed that the sense of stereoinduction, namely (R)-product from with (3R)-1-benzyl-3-(arylthio)pyrrolidine is in agreement with the nucleophilic attack being directed at the allylic carbon located trans to the sulfur atom in the intermediate eta(3)-allylpalladiuln complex. (C) 2004 Elsevier Ltd. All rights reserved.