(3S,4S)-3,4-bis(tert-butyldimethylsilyloxy)-1-pyrroline N-oxide | 180139-81-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯啉
• 英文名称: (3S,4S)-3,4-bis(tert-butyldimethylsilyloxy)-1-pyrroline N-oxide
• 英文别名: tert-butyl-[[(3S,4S)-3-[tert-butyl(dimethyl)silyl]oxy-1-oxido-3,4-dihydro-2H-pyrrol-1-ium-4-yl]oxy]-dimethylsilane
• CAS: 180139-81-5
• 化学式: C₁₆H₃₅NO₃Si₂
• 分子量: 345.63
• InChiKey: LUPGAOCHWIIQQD-KBPBESRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.36
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  47.2
• 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-bis(tert-butyldimethylsilyloxy)-1-pyrroline N-oxide 以 邻二氯苯 、 苯 为溶剂， 反应 267.0h， 生成 1-[(3S,4S)-3,4-Bis-(tert-butyl-dimethyl-silanyloxy)-pyrrolidin-(2Z)-ylidene]-butan-2-one
  参考文献：
  名称：

  (1S,2S,7R,8aS)- and (1S,2S,7S,8aS)-trihydroxyoctahydroindolizine: Two new glycosidase inhibitors by nitrone cycloaddition strategy

  摘要：

  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

  DOI：

  10.1016/0957-4166(96)00200-5
• 作为产物：
  描述：

  tert-butyl-[[(3S,4S)-3-[tert-butyl(dimethyl)silyl]oxy-3,4-dihydro-2H-pyrrol-4-yl]oxy]-dimethylsilane 在 urea hydrogen peroxide 、 甲基三氧化铼(VII) 作用下， 以 甲醇 为溶剂， 反应 1.5h， 以50%的产率得到(3S,4S)-3,4-bis(tert-butyldimethylsilyloxy)-1-pyrroline N-oxide
  参考文献：
  名称：

  基于甲基三氧合hen /脲过氧化氢的亚胺的催化氧化：温和且易于化学和区域选择性地进入硝酮。

  摘要：

  [反应：见正文]报道了第一个成功的催化氧化过程，用于将亚胺化学选择性转化为硝酮。该反应是一般的，高产率的并且是用户和环境友好的，并且提供了对于尚未解决的问题的解决方案，该问题是通过氮衍生物的氧化来选择性地进入硝酮。

  DOI：

  10.1021/ol062862w

文献信息

• Effective Oxidation of Secondary Amines to Nitrones with Alkyl Hydroperoxides Catalysed by (Trialkanolaminato)titanium(IV) Complexes
  作者：Massimiliano Forcato、Miriam Mba、William A. Nugent、Giulia Licini

  DOI：10.1002/ejoc.200900867

  日期：2010.2

  The effective catalytic oxidation of secondary amines to nitrones with alkyl hydroperoxides as the primary oxidants is described. The titanium alkoxide catalysts are protected from the water co-product by the combined use of a tightly binding trialkanolamine ligand and molecular sieves. Nitrones can be obtained in high yields (up to 98 %) under homogeneous, anhydrous conditions and even in the absence

  描述了使用烷基氢过氧化物作为主要氧化剂将仲胺有效催化氧化为硝酮的过程。通过结合使用紧密结合的三烷醇胺配体和分子筛，可以保护钛醇盐催化剂免受水副产物的影响。在均相、无水条件下，甚至在没有溶剂的情况下，都能以高产率（高达 98%）获得硝酮。反应速度快（2-7 小时），只需 1% 的催化剂即可实现良好的选择性和完全转化。
• 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。
• Polyhydroxypyrrolidine Glycosidase Inhibitors Related to (+)-Lentiginosine
  作者：Francesca Cardona、Andrea Goti、Sylviane Picasso、Pierre Vogel、Alberto Brandi

  DOI：10.1080/07328300008544101

  日期：2000.1

  (+)-Lentiginosine (14) and (7R)-7-hydroxylentiginosine (26), powerful inhibitors of amyloglucosidases, and their enantiomers were obtained in high overall yields by a multistep synthesis involving 1,3-dipolar cycloaddition of enantiopure tartaric acid derived pyrroline N-oxides. Structurally related (S,S)-3,4-dihydroxypyrrolidines 29-33 were synthesized as simpler models and tested towards 24 glycosidases.

  (+)-Lentiginosine（14）和（7R)-7-羟基lentiginosine（26）及其对映体作为高活性的淀粉葡萄糖苷酶抑制剂，通过多步合成路线，从结构明确的酒石酸衍生的吡咯啉N-氧化物出发，经1,3-偶极环加成反应，以较高总产率成功获得。此外，合成了一系列结构相关的(S,S)-3,4-二羟基吡咯啶（29-33）作为简化模型，并对24种糖苷酶进行了活性测试。
• Catalytic Oxidation of Imines Based on Methyltrioxorhenium/Urea Hydrogen Peroxide:  A Mild and Easy Chemo- and Regioselective Entry to Nitrones
  作者：Gianluca Soldaini、Francesca Cardona、Andrea Goti

  DOI：10.1021/ol062862w

  日期：2007.2.1

  [reaction: see text] The first successful catalytic oxidation procedure for the chemoselective conversion of imines to nitrones is reported. The reaction is general, high yielding, and user and environmentally friendly, and furnishes a solution to the yet unanswered issue of regioselective access to nitrones by oxidation of nitrogen derivatives.

  [反应：见正文]报道了第一个成功的催化氧化过程，用于将亚胺化学选择性转化为硝酮。该反应是一般的，高产率的并且是用户和环境友好的，并且提供了对于尚未解决的问题的解决方案，该问题是通过氮衍生物的氧化来选择性地进入硝酮。
• (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