(2S,5S)-bis(methoxymethoxymethyl)pyrrolidine | 93621-95-5

• 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: (2S,5S)-bis(methoxymethoxymethyl)pyrrolidine
• 英文别名: (2s,5s)-2,5-Bis(methoxymethoxy-methyl)pyrrolidine；(2S,5S)-2,5-bis(methoxymethoxymethyl)pyrrolidine
• CAS: 93621-95-5
• 化学式: C₁₀H₂₁NO₄
• 分子量: 219.281
• InChiKey: AZSOHULVQDDQGO-UWVGGRQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  15
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  49
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2S,5S)-bis(methoxymethoxymethyl)pyrrolidine 在 4-二甲氨基吡啶 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 二氯甲烷 为溶剂， 生成 (2S,5S)-N-<(S)-N-bis(methylthio)methylenevalyl>-2,5-bis(methoxymethoxymethyl)pyrrolidine
  参考文献：
  名称：

  Asymmetric synthesis of α-amino acids by alkylation of a glycine amide derivative bearing chiral 2,5-disubstituted pyrrolidine as an amine component

  摘要：

  DOI：

  10.1016/s0040-4039(00)84807-8
• 作为产物：
  描述：

  1-<(S)-1-Phenylethyl>-2,5-cis-bis(methoxycarbonyl)pyrrolidine 在 palladium dihydroxide lithium aluminium tetrahydride 、 氢气 、 sodium methylate 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 25.0 ℃ 、303.98 kPa 条件下， 反应 21.5h， 生成 (2S,5S)-bis(methoxymethoxymethyl)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

• 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。
• Development of Guanidine-Bisurea Bifunctional Organocatalysts with a Chiral Pyrrolidine Moiety and Application to α-Hydroxylation of Tetralone-Derived β-Keto Esters
  作者：Minami Odagi、Kan Takayama、Makoto Sato、Masahiro Yamanaka、Kazuo Nagasawa

  DOI：10.3390/molecules200712590

  日期：——

  guanidine-bisurea bifunctional organocatalysts 5 bearing a chiral pyrrolidine moiety on guanidine were designed with the guidance of DFT calculations. The resulting organocatalysts 5 were examined for α-hydroxylation of tetralone-derived β-keto esters, and good selectivity was obtained with 5j bearing a methoxymethyl ether-containing chiral pyrrolidine moiety.

  在DFT计算的指导下，设计了在胍上带有手性吡咯烷部分的新型胍-双脲双功能有机催化剂5。检查得到的有机催化剂5的四氢萘酮衍生的β-酮酯的α-羟基化，并且用带有含甲氧基甲基醚的手性吡咯烷部分的5j获得了良好的选择性。
• Synthetic studies towards the octahydro-1H-benzo[f]pyrrolo[3,2,1-ij]quinolines: enantioselective synthesis of (2R,3S)-2-[(1S)-3-(benzyloxy)-1-(tert-butyldimethyl-silyloxymethyl)propyl]-3-phenylhexahydropyridine
  作者：George S Zaponakis、Haralambos E Katerinopoulos

  DOI：10.1016/s0040-4039(01)01260-6

  日期：2001.9

  for the preparation of (6aS,11bS,11cS)-1H-benzo[f]pyrrolo[3,2,1-ij]quinoline—was synthesized in nine steps. The synthetic approach uses both enantiomers of the chiral auxiliary trans-2,5-bis(methoxymethoxymethyl)pyrrolidine, employed in different stages of the synthesis for the construction of two out of the three stereogenic centers in the above mentioned intermediate.

  （2 R，3 S）-2-[（1 S）-3-（苯甲氧基）-1-（叔丁基二甲基甲硅烷基氧甲基）丙基] -3-苯基六氢吡啶-（6 a S，11b S的关键合成中间体通过9个步骤合成了，11c S）-1 H-苯并[ f ]吡咯并[3,2,1- ij ]喹啉。合成方法使用手性辅助反式-2,5-双（甲氧基甲氧基甲基）吡咯烷的两种对映异构体，它们在合成的不同阶段用于在上述中间体中的三个立体异构中心中的两个构建。
• Symmetry-Assisted Synthesis of <i>C</i>₂-Symmetric <i>trans</i>-α,α‘-Bis(hydroxymethyl)pyrrolidine and -piperidine Derivatives via Double Sharpless Asymmetric Dihydroxylation of α,ω-Terminal Dienes
  作者：Hiroki Takahata、Seiki Takahashi、Shin-ichi Kouno、Takefumi Momose

  DOI：10.1021/jo971995f

  日期：1998.4.1

  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.
• Asymmetric synthesis of α-amino acids by alkylation of a glycine amide derivative bearing chiral 2,5-disubstituted pyrrolidine as an amine component
  作者：Satoru Ikegami、Takashi Hayama、Tsutomu Katsuki、Masar-u Yamaguchi

  DOI：10.1016/s0040-4039(00)84807-8

  日期：1986.1