(3S,4s)-3,4-双[[(1,1-二甲基乙基)二甲基甲硅烷基]氧基]-1-(苯基甲基)-吡咯烷 | 138228-45-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: (3S,4s)-3,4-双[[(1,1-二甲基乙基)二甲基甲硅烷基]氧基]-1-(苯基甲基)-吡咯烷
• 英文名称: (3S,4S)-1-benzyl-3,4-bis(tert-butyldimethylsilyloxy)-pyrrolidine
• 英文别名: (3S,4S)-1-Benzyl-3,4-bis((tert-butyldimethylsilyl)oxy)pyrrolidine；[(3S,4S)-1-benzyl-4-[tert-butyl(dimethyl)silyl]oxypyrrolidin-3-yl]oxy-tert-butyl-dimethylsilane
• CAS: 138228-45-2
• 化学式: C₂₃H₄₃NO₂Si₂
• 分子量: 421.771
• InChiKey: LLGNPRXNMNDZSO-SFTDATJTSA-N

物化性质

• 沸点：
  414.5±45.0 °C(Predicted)
• 密度：
  0.95±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.28
• 重原子数：
  28
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  21.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3S,4s)-3,4-双[[(1,1-二甲基乙基)二甲基甲硅烷基]氧基]-1-(苯基甲基)-吡咯烷 在 palladium dihydroxide N-氯代丁二酰亚胺 、 氢气 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲醇 、 乙醚 、 苯 为溶剂， 25.0 ℃ 、405.3 kPa 条件下， 反应 8.0h， 生成 tert-butyl-[[(3S,4S)-3-[tert-butyl(dimethyl)silyl]oxy-3,4-dihydro-2H-pyrrol-4-yl]oxy]-dimethylsilane
  参考文献：
  名称：

  Synthesis of (3S,4S)-3,4-Dihydroxyprolines from L-Tartaric Acid.

  摘要：

  通过环状席夫碱的氰基甲硅烷基化，由 L-酒石酸合成了天然 (2S, 3S, 4S)-3, 4-二羟基脯氨酸 (1) 和新的 (2R, 3S, 4S)-异构体 (7)。

  DOI：

  10.1248/cpb.39.2219
• 作为产物：
  描述：

  (3R,4R)-3,4-Bis<(tert-butyldimethylsilyl)oxy>-1-benzyl-2,5-pyrrolidinedione 在 硼烷四氢呋喃络合物 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 21.0h， 以93%的产率得到(3S,4s)-3,4-双[[(1,1-二甲基乙基)二甲基甲硅烷基]氧基]-1-(苯基甲基)-吡咯烷
  参考文献：
  名称：

  含吡咯烷-1-基的铑类胡萝卜素的意外重排

  摘要：

  酮-和酯-取代的重氮化合物，其含有吡咯烷部分用二铑四乙产生相应的铑卡宾处理。期望它们插入吡咯烷部分的CH键中，但是反应不同。酮-取代铑卡宾体经历了沃尔夫重排。将得到的烯酮继续通过内酰胺和环电环反应-开口，给丙烯酰胺。酯-取代的铑卡宾体进行了[1.2] -的（吡咯烷的移位- 1 -甲基）部分，得到甲基丙烯酸酯。对于每种重排，都建议一种机制。

  DOI：

  10.1016/j.tetlet.2014.02.132

文献信息

• Low-generation dendrimers with a calixarene core and based on a chiral <i>C</i>₂-symmetric pyrrolidine as iminosugar mimics
  作者：Marco Marradi、Stefano Cicchi、Francesco Sansone、Alessandro Casnati、Andrea Goti

  DOI：10.3762/bjoc.8.107

  日期：——

  The preparation of low-generation dendrimers based on a simple calix[4]arene scaffold by insertion of the iminosugar-analogue C₂-symmetric 3,4-dihydroxypyrrolidine is described. This methodology allows a rapid incorporation of a considerable number of iminosugar-like moieties in a reduced volume and in a well-defined geometry. The inclusion of alkali-metal ions (sodium and potassium) in the polar cavity defined by the acetamide moieties at the lower rim of the calixarene was demonstrated, which allows also the rigidification of the dendrimer structure and the iminosugar presentation in the clusters. The combination of the supramolecular properties of calixarenes with the advantage of a dendrimeric presentation of repetitive units opens up the possibility of generating well-defined multivalent and multifaceted systems with more complex and/or biologically relevant iminosugars.

  基于简单的杯[4]芳烃支架制备低代数树状聚合物，通过插入类似亚胺糖的C2对称3,4-二羟基吡咯烷来实现。这种方法允许在较小的体积和明确定义的几何形状中快速引入大量类似亚胺糖的基团。在杯芳烃底部的乙酰胺基团定义的极性腔中展示了碱金属离子（钠和钾）的包容，这也使得树状聚合物结构变得更加刚性，并在团簇中呈现亚胺糖。将杯芳烃的超分子特性与树状聚合物呈现重复单元的优势相结合，为生成具有更复杂和/或生物相关亚胺糖的明确定义多价和多方面系统打开了可能性。
• New enantiomerically pure oligomeric macrocycles based on a 3,4-dihydroxypyrrolidine nucleus
  作者：Stefano Cicchi、Elisa Chierroni、Andrea Goti、Alberto Brandi、Annalisa Guerri、Pierluigi Orioli

  DOI：10.1039/a703583g

  日期：——

  (3S,4S)-N-Benzyl-3,4-dihydroxypyrrolidine 1 has been used as a building block for new enantiopure macrocyclic polyesters. Two different synthetic approaches are presented leading to complementary results. The structure of the macrocycles synthesized has been confirmed by NMR spectroscopy and FAB mass spectrometry, and that for dimer 8 has been confirmed by X-ray analysis.

  (3S,4S)-N-苄基-3,4-二羟基吡咯烷 1 被用作新的对映体纯大环聚酯的构建基块。两种不同的合成方法产生了互补的结果。合成的大环的结构已通过核磁共振光谱和 FAB 质谱法得到证实，二聚体 8 的结构已通过 X 射线分析得到证实。
• Copper-Catalyzed Synthesis of a Highly Hydroxy-Functionalized Benzo[<i>e</i>]indolizidine by Intramolecular<i>N</i>-Arylation
  作者：Franca M. Cordero、Bhushan B. Khairnar、Paola Bonanno、Andrea Martinelli、Alberto Brandi

  DOI：10.1002/ejoc.201300440

  日期：2013.8

  5S)-1,2,3,3a,4,5-hexahydropyrrolo[1,2-a]quinoline-2,3,5-triol (2,3,5-trihydroxybenzo[e]indolizidine) framework has been synthesized by a straightforward strategy consisting of 1,3-dipolar cycloaddition of a pyrroline N-oxide to 2-bromostyrene followed by isoxazolidine N–O bond reduction and cyclization by copper-catalyzed nucleophilic aromatic substitution of the intermediate pyrrolidine.

  对映体纯 (2S,3S,3aS,5S)-1,2,3,3a,4,5-六氢吡咯并[1,2-a]quinoline-2,3,5-triol (2,3,5-trihydroxybenzo[ e]indolizidine) 框架是通过一种简单的策略合成的，该策略包括吡咯啉 N-氧化物与 2-溴苯乙烯的 1,3-偶极环加成，然后通过铜催化的中间体的亲核芳香取代异恶唑烷 N-O 键还原和环化吡咯烷。
• Chiral Hemilabile P,N‐Ligand‐Assisted Gold Redox Catalysis for Enantioselective Alkene Aminoarylation
  作者：Xiaohan Ye、Chenhuan Wang、Shuyao Zhang、Qi Tang、Lukasz Wojtas、Minyong Li、Xiaodong Shi

  DOI：10.1002/chem.202201018

  日期：2022.6.15

  Enantioselective, intermolecular alkene arylamination was achieved through gold redox catalysis. Screening of ligands revealed chiral P,N ligands as the optimal choice, giving alkene aminoarylation with good yields (up to 80 %) and excellent stereoselectivity (up to 99 : 1 er). As the first example of enantioselective gold redox catalysis, this work confirmed the feasibility of applying a chiral ligand

  通过金氧化还原催化实现了对映选择性分子间烯烃芳基化。配体筛选显示手性 P,N 配体是最佳选择，可使烯烃氨基芳基化具有良好的收率（高达 80%）和出色的立体选择性（高达 99 : 1 er）。作为对映选择性金氧化还原催化的第一个例子，这项工作证实了在金（I）阶段应用手性配体的可行性，并在金（III）中间体进行立体决定步骤（SDS），从而开辟了一条新途径用立体化学控制进行金氧化还原催化。
• (1S,2S,7R,8aS)- and (1S,2S,7S,8aS)-trihydroxyoctahydroindolizine: Two new glycosidase inhibitors by nitrone cycloaddition strategy
  作者：Andrea Goti、Francesca Cardona、Alberto Brandi、Sylviane Picasso、Pierre Vogel

  DOI：10.1016/0957-4166(96)00200-5

  日期：1996.6

  The two new epimeric (1S,2S,7R,8aS)- and (1S,2S,7S,8aS)-1,2,7-trihydroxyoctahydroindolizines 4 and 5 have been synthesized via methylenecyclopropane-nitrone cycloaddition-rearrangement methodology employing an enantiomerically pure L-tartaric acid derived nitrone 7b. Highly stereoselective reductions of the intermediate indolizidinone 10b and final deprotection furnished the two title indolizidinetriols 4 and 5, the inhibiting abilities of which toward 24 commercially available glycosidases were tested. Both 4 and 5 are good competitive inhibitors of amyloglucosidases with K-i values of ca. 6 and 75 mu M, respectively. Compared with (+)-lentiginosine 3, 4 and 5 are less powerful inhibitors but, in contrast to 3, the (7R)-hydroxy analogue 4 possesses a weak inhibiting activity toward alpha-L-fucosidase from bovine epididymis. A model to rationalize the structure-activity relationship of (+)-lentiginosine and the two new 7-hydroxylentiginosines toward glucoamylases is proposed on the basis of their structural comparison with known inhibitors and with the natural enzyme's substrate amylose. Copyright (C) 1996 Elsevier Science Ltd