1-Benzyl-[(2R,5R)-2,5-bis(hydroxymethyl)]pyrrolidine | 93713-36-1

• 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: 1-Benzyl-[(2R,5R)-2,5-bis(hydroxymethyl)]pyrrolidine
• 英文别名: N-benzyl-trans-(2R,5R)-bis(hydroxymethyl)-pyrrolidine；trans-(1-Benzylpyrrolidine-2,5-diyl)dimethanol；[(2R,5R)-1-benzyl-5-(hydroxymethyl)pyrrolidin-2-yl]methanol
• CAS: 93713-36-1
• 化学式: C₁₃H₁₉NO₂
• 分子量: 221.299
• InChiKey: KDHJNPHFSBLEMM-CHWSQXEVSA-N

物化性质

• 沸点：
  358.7±12.0 °C(Predicted)
• 密度：
  1.133±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  43.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-Benzyl-[(2R,5R)-2,5-bis(hydroxymethyl)]pyrrolidine 在 氯化亚砜 作用下， 生成 (+)-N-benzyl-(2S,5S)-2,5-diethylpyrrolidine
  参考文献：
  名称：

  Enantioselective palladium catalyzed allylic alkylation with C2-symmetric chiral diamine ligands

  摘要：

  A C-2-symmetric chiral diamine ligand 1 was found to be effective for palladium catalyzed asymmetric allylic substitution of racemic 1,3-diphenyl-2-propenyl acetate 5 with dimethyl malonate. The X-ray analysis and NMR study of the palladium complex 7 with chiral diamine 1 have revealed the mechanism of high enantioselection.

  DOI：

  10.1016/s0040-4039(00)61472-7
• 作为产物：
  描述：

  1,2,5,6-四羟基己烷 在 咪唑 、 盐酸 、 4-二甲氨基吡啶 、 三乙胺 作用下， 生成 1-Benzyl-[(2R,5R)-2,5-bis(hydroxymethyl)]pyrrolidine
  参考文献：
  名称：

  Symmetry-Assisted Synthesis of C₂-Symmetric trans-α,α‘-Bis(hydroxymethyl)pyrrolidine and -piperidine Derivatives via Double Sharpless Asymmetric Dihydroxylation of α,ω-Terminal Dienes

  摘要：

  A new strategy has been developed for the synthesis of C-2-symmetric trans-alpha,alpha'-bis(hydroxymethyl)pyrrolidine and piperidine derivatives 1-3 starting from symmetric alpha,omega-terminal dienes 4-6. The double-asymmetric dihydroxylation (AD) reaction of 4-6 gave C-2-symmetric tetrols, which were converted in a four-step sequence to C-2-symmetric azacycloalkanes 17, 9, and 22, respectively. These azacycloalkanes were transformed into 1-3 in high enantiomeric excess (82% --> 98%ee). The double AD reaction proved to cause enantiomeric enhancement, even though the asymmetric induction for the first AD reaction is moderate. In addition, it was observed that the chromatography on silica gel of several C-2-symmetric azacycloalkanes (17, 20, and 22) of varying ee's resulted in marked enantiomeric fractionation.

  DOI：

  10.1021/jo971995f

文献信息

• Synthesis of enantiomerically pure (2R, 5R) disubstituted pyrrolidines from D-mannitol
  作者：M. Marzi、P. Minetti、D. Misiti

  DOI：10.1016/s0040-4020(01)89042-6

  日期：——

  Pyrrolidines and are obtained from D-Mannitol, giving good total yields and in an enantiomerically pure form. Some comments and studies regarding pyrrolidine ring closure (key step) are also reported.

  从D-甘露糖醇中得到的吡咯烷和，具有良好的总收率和对映体纯的形式。还报道了一些有关吡咯烷环闭合（关键步骤）的评论和研究。
• Asymmetric alkylation of carboxyamides by using trans-2,5-disubstituted pyrrolidines as chiral auxiliaries
  作者：Yasuhiro Kawanami、Yoshio Ito、Toshiyuki Kitagawa、Yoshiyuki Taniguchi、Tsutomu Katsuki、Masaru Yamaguchi

  DOI：10.1016/s0040-4039(01)80046-0

  日期：1984.1

  trans-2,5-Bis(methoxymethyl)- and trans-2,5-bis(methoxymethoxymethyl)pyrrolidines proved to be excellent chiral auxiliaries for the asymmetric alkylation of the corresponding carboxyamide enolates giving good chemical yield and high stereoselectivity (invariably over 95% de), with remarkable flexibility to substrates and reaction conditions.

  反式-2,5-双（甲氧基甲基）-和反式-2,5-双（甲氧基甲氧基甲基）吡咯烷酮是出色的手性助剂，用于相应的羧酰胺烯酸酯的不对称烷基化，具有良好的化学收率和较高的立体选择性（始终超过95％ de），对底物和反应条件具有显着的灵活性。
• Asymmetric cycloaddition of anthrone and maleimides catalyzed by C2-chiral pyrrolidines
  作者：Kouhei Uemae、Satoshi Masuda、Yukio Yamamoto

  DOI：10.1039/b100961n

  日期：——

  Catalytic asymmetric cycloaddition of anthrone with N-alkyl- and N-arylmaleimides with various substituents in the aromatic ring was carried out in the presence of C2-chiral pyrrolidines to afford chiral, non-racemic [4 + 2] adducts. Among them, good catalytic activity was observed with the pyrrolidines with a N-(4-pyridyl)methyl group 1h, which was discussed from the viewpoint of conformational analysis. The best stereoselectivity of 87% ee was attained when the reaction of N-(2-tert-butylphenyl)maleimide 4j and anthrone was promoted with 1h.

  在 C2 手性吡咯烷存在下，蒽酮与芳香环上具有不同取代基的 N-烷基和 N-芳基马来酰亚胺进行了催化不对称环加成反应，得到了手性非外消旋 [4 + 2] 加合物。其中，带有 N-（4-吡啶基）甲基的吡咯烷类化合物 1h 具有良好的催化活性，并从构象分析的角度对其进行了讨论。用 1h 促进 N-(2-叔丁基苯基)马来酰亚胺 4j 和蒽酮的反应，可获得 87%ee 的最佳立体选择性。
• Synthesis of both enantiomers of C2 symmetric trans-2,5-bis(hydroxymethyl)pyrrolidine. Lipase mediated sequential kinetic resolutions
  作者：Mukund P. Sibi、JianLiang Lu

  DOI：10.1016/s0040-4039(00)73281-3

  日期：1994.7

  Lipase mediated sequential kinetic resolution has been employed to give both enantiomers of trans-2,5-bis(hydroxymethyl)pyrrolidine in optically pure form. The effect of different parameters on the ee and yields in these resolutions are also reported.

  脂肪酶介导的顺序动力学拆分已被用于以光学纯的形式给出反式-2,5-双（羟甲基）吡咯烷的两种对映异构体。还报告了这些分辨率中不同参数对ee和产量的影响。
• Design and synthesis of novel chiral pyrrolidine-based diamines with C2-symmetry
  作者：Makoto Nakajima、Kiyoshi Tomioka、Kenji Koga

  DOI：10.1016/s0040-4020(01)80176-9

  日期：1993.1

  Novel chiral pyrrolidine-based diamines with C2-symmetry 2, 3 and their related compounds 4 - 8 were designed and synthesized in optically pure forms. Both (+)- and (-)-2 were prepared from optical active ditosylate 9. 3 was prepared from 3,5-dimethylbenzaldehyde through optical resolution and its absolute stereochemistry was correlated with 2,3-dimethylsuccinate 27. 4 was prepared from (-)-diol 28. 5 - 8 were prepared from 9 and 11.