1-[(S)-1-phenylethyl]-(2R,5R)-bis(methoxycarbonyl)pyrrolidine | 134860-27-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1-[(S)-1-phenylethyl]-(2R,5R)-bis(methoxycarbonyl)pyrrolidine
• 英文别名: 1-<(S)-1'-phenylethyl>-(2R,5R)-bis(methoxycarbonyl)pyrrolidine；1-<(S)-1-Phenylethyl>-2,5-(R,R)-bis(methoxycarbonyl)pyrrolidine；dimethyl (2R,5R)-1-[(1S)-1-phenylethyl]pyrrolidine-2,5-dicarboxylate
• CAS: 134860-27-8
• 化学式: C₁₆H₂₁NO₄
• 分子量: 291.347
• InChiKey: RJYITRDYEYZDCW-IACUBPJLSA-N

物化性质

• 沸点：
  357.0±42.0 °C(Predicted)
• 密度：
  1.162±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-[(S)-1-phenylethyl]-(2R,5R)-bis(methoxycarbonyl)pyrrolidine 在 palladium dihydroxide 氢气 、 sodium cyanoborohydride 、 溶剂黄146 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 30.0h， 生成 dimethyl (2R,5R)-1-methylpyrrolidine-2,5-dicarboxylate
  参考文献：
  名称：

  Chiral C2-symmetric 2,5-disubstituted pyrrolidine derivatives as chiral catalyst ligands in the reaction of diethylzinc with arylaldehydes

  摘要：

  Two kinds of chiral C-2-symmetric 2,5-disubstituted pyrrolidine derivatives having a beta-aminoalcohol moiety were successfully synthesized and their catalytic abilities of asymmetric induction were examined in the reaction of diethylzinc with arylaldehydes. The production of sec-alcohols in high yields and high enantiomeric excesses having the R-configuration could be achieved when N-(2',2'-diphenyl-2'-hydroxyethyl)-(2R, 5R) -bis(methoxymethyl)pyrrolidine was used as a chiral ligand. On the other hand, when N-methyl-(2R, 5R)-bis(diarylhydroxymethyl)pyrrolidine was used as a catalyst, the enantiomeric excesses of the sec-alcohols went down and the inversion of the enantioselectivity was observed in the reaction of m-chloro-, p-chloro-, and m-fluorobenzaldehyde with diethylzinc.

  DOI：

  10.1016/0957-4166(95)00276-u
• 作为产物：
  描述：

  1-<(S)-1-Phenylethyl>-2,5-cis-bis(carboxy)pyrrolidine 在 氯化亚砜 、 sodium methylate 作用下， 以 正己烷 为溶剂， 反应 8.0h， 生成 1-[(S)-1-phenylethyl]-(2R,5R)-bis(methoxycarbonyl)pyrrolidine
  参考文献：
  名称：

  A Convenient Synthesis of Enantiomeric Pairs of 2,5-Disubstituted Pyrrolidines of C₂-Symmetry

  摘要：

  通过使用 (-)-1-苯基乙胺作为手性辅助剂，从二甲基阳离子-2,5-二溴己二酸酯制备了三种二叠体异构体的 2,5-双(甲氧基羧基)吡咯烷衍生物，并通过结晶和涉及立体选择性水解的色谱分离进行分离。收回顺式异构体并使其异构化为反式异构体。从每种反式异构体出发，通过一种简短的路线合成了具有 C2 对称性的光学活性 2,5-二取代的 [2,5-双(甲氧基甲基)和 2,5-双(甲氧基甲氧基甲基)] 吡咯烷。

  DOI：

  10.1055/s-1993-25852

文献信息

• Synthesis of a Conformationally Rigid Analogue of 2-Aminoadipic Acid ­Containing an 8-Azabicyclo[3.2.1]octane Skeleton
  作者：Pavel Mykhailiuk、Vladimir Kubyshkin、Anne Ulrich、Igor Komarov

  DOI：10.1055/s-0029-1216963

  日期：2009.10

  A new, conformationally rigid analogue of 2-amino­adipic acid, 8-[(benzyloxy)carbonyl]-3-methylene-8-azabicyclo[3.2.1]octane-1,5-dicarboxylic acid, is synthesized from dimethyl rac-2,5-dibromohexanedioate. The key steps involve alkylation-cyclization of 1-benzyl 2,5-dimethyl pyrrolidine-1,2,5-tricarboxylate with 3-chloro-2-(chloromethyl)prop-1-ene to yield the 8-azabicyclo[3.2.1]octane skeleton.

  一种新型构象刚性的2-氨基己二酸类似物，即8-[(苄氧基)羰基]-3-亚甲基-8-氮杂双环[3.2.1]辛烷-1,5-二羧酸，由外消旋二甲基2,5-二溴己二酸酯合成。关键步骤包括1-苄基2,5-二甲基吡咯烷-1,2,5-三羧酸酯与3-氯-2-(氯甲基)丙-1-烯的烷基化-环化反应，生成8-氮杂双环[3.2.1]辛烷骨架。
• Synthesis of Fmoc- and Boc-Protected (2S,5S)- and (2R,5R)-5-Aminomethylprolines
  作者：Markus Heinrich、Amelie Bartuschat、Nina Hegmann

  DOI：10.1055/s-0037-1610304

  日期：2019.2

  building blocks for peptides since they allow conformational fixation of peptidyl–CO–N-prolyl bonds in the unusual cis conformation. The stereoselective syntheses of these dimethylaminomethyl-prolines is achieved from literature-known precursors with overall yields of 23% [over 8 steps for (2S,5S)dmamPro], 33% [over 9 steps for (2S,5S)N-Boc-amPro] and 12% [over 8 steps for (2R,5R)dmamPro]. The applicability

  摘要 脯氨酸衍生物（2 S，5 S）dmamPro，（2 S，5 S）N -Boc-amPro和（2 R，5 R）dmamPro是肽的有用构建基块，因为它们可以使肽基–CO–N进行构象固定-脯氨酸键以不寻常的顺式构象存在。这些二甲基氨基甲基脯氨酸的立体选择性合成是从文献已知的前体中实现的，总收率为23％[（2 S，5 S）dmamPro的8步]，33％[（2 S，5 S的9步）N -Boc-amPro]和12％[对于（2 R，5R）dmamPro]。通过制备Fmoc-Val-amPro-OMe二肽证明了（2 S，5 S）N -Boc-amPro在肽合成中的适用性。 脯氨酸衍生物（2 S，5 S）dmamPro，（2 S，5 S）N -Boc-amPro和（2 R，5 R）dmamPro是肽的有用构建基块，因为它们可以使肽基–CO–N进行构象固定-脯氨酸键以不寻常的顺式构象存在。这些二甲基氨
• Synthesis of new, highly hindered C2-symmetric trans-(2S,5S)-disubstituted pyrrolidines
  作者：Varinder K. Aggarwal、Franck Sandrinelli、Jonathan P.H. Charmant

  DOI：10.1016/s0957-4166(02)00032-0

  日期：2002.2

  trans-(2S.5S)-(1,1-Diphenylmethyl)pyrrolidine has been prepared from the corresponding diester in four steps and 54% overall yield. Key steps involve the nucleophilic addition of an organomagnesium reagent to a carbonyl compound promoted by cerium(III) chloride and the reductive removal of benzylic trimethylsilyloxyl groups with Me3SiCl-Nal-MeCN and water. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Shi, Min; Inoue, Yoshihisa, Journal of the Chemical Society. Perkin Transactions 2 (2001), 1998, # 8, p. 1725 - 1729
  作者：Shi, Min、Inoue, Yoshihisa

  DOI：——

  日期：——
• Chiral C2-symmetric 2,5-disubstituted pyrrolidine derivatives as chiral catalyst ligands in the reaction of diethylzinc with arylaldehydes
  作者：Min Shi、Yukihiro Satoh、Takechi Makihara、Yukio Masaki

  DOI：10.1016/0957-4166(95)00276-u

  日期：1995.9

  Two kinds of chiral C-2-symmetric 2,5-disubstituted pyrrolidine derivatives having a beta-aminoalcohol moiety were successfully synthesized and their catalytic abilities of asymmetric induction were examined in the reaction of diethylzinc with arylaldehydes. The production of sec-alcohols in high yields and high enantiomeric excesses having the R-configuration could be achieved when N-(2',2'-diphenyl-2'-hydroxyethyl)-(2R, 5R) -bis(methoxymethyl)pyrrolidine was used as a chiral ligand. On the other hand, when N-methyl-(2R, 5R)-bis(diarylhydroxymethyl)pyrrolidine was used as a catalyst, the enantiomeric excesses of the sec-alcohols went down and the inversion of the enantioselectivity was observed in the reaction of m-chloro-, p-chloro-, and m-fluorobenzaldehyde with diethylzinc.