N'-methyl-N'-methoxy-N-tosylalaninamide | 1019853-13-4

• 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: N'-methyl-N'-methoxy-N-tosylalaninamide
• 英文别名: (S)-N-methoxy-N-methyl-2-(4-methylphenylsulfonamido)propanamide；(S)-N-methoxy-N-methyl-2-(4-methylphenylsulfonamide)propanamide；weinreb amide of N-tosylalanine；(S)-N-methoxy-N-methyl-2-(toluene-4-sulfonylamino)-propionamide；(2S)-N-methoxy-N-methyl-2-[(4-methylphenyl)sulfonylamino]propanamide
• CAS: 1019853-13-4
• 化学式: C₁₂H₁₈N₂O₄S
• 分子量: 286.352
• InChiKey: KFFHQTMYKYFINP-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  84.1
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  N'-methyl-N'-methoxy-N-tosylalaninamide 在 lithium aluminium tetrahydride 、 sodium hydride 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 、 甲苯 、 xylene 为溶剂， 反应 4.67h， 生成 (2R,4aR,7S,7aR)-4-oxo-6-tosyl-1,2,7-trimethyloctahydro-1H-pyrrolo[3,4-b]pyridine
  参考文献：
  名称：

  Diastereoselective cycloaddition of alkylidenecyclopropane nitrones from palladium(0)-catalyzed nucleophilic substitution of asymmetric 1-alkenylcyclopropyl esters by amino acids

  摘要：

  The asymmetric construction of perhydropyrrolo[3,4-b]pyridine derivatives was performed by chemo- and regioselective formation of enantiopure alkylidenecyclopropane nitrones, followed by diastereoselective intramolecular 1,3-dipolar cycloaddition. The resulting spirocyclopropane isoxazolidines then underwent thermally induced regioselective ring expansion into optically active diazaheterocycles. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00006-9
• 作为产物：
  描述：

  二甲羟胺盐酸盐 、 (S)-2-(4-甲基苯基磺酰胺基)丙酸甲酯 在 吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 以74%的产率得到N'-methyl-N'-methoxy-N-tosylalaninamide
  参考文献：
  名称：

  Diastereoselective cycloaddition of alkylidenecyclopropane nitrones from palladium(0)-catalyzed nucleophilic substitution of asymmetric 1-alkenylcyclopropyl esters by amino acids

  摘要：

  The asymmetric construction of perhydropyrrolo[3,4-b]pyridine derivatives was performed by chemo- and regioselective formation of enantiopure alkylidenecyclopropane nitrones, followed by diastereoselective intramolecular 1,3-dipolar cycloaddition. The resulting spirocyclopropane isoxazolidines then underwent thermally induced regioselective ring expansion into optically active diazaheterocycles. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00006-9

文献信息

• Copper(II) Triflate-Catalyzed Intramolecular Hydroamination of Homoallylic Amino Alcohols as an Expedient Route to trans-2,5-Dihydro-1H-pyrroles and 1,2-Dihydroquinolines
  作者：Weidong Rao、Prasath Kothandaraman、Chii Boon Koh、Philip Wai Hong Chan

  DOI：10.1002/adsc.201000450

  日期：2010.10.4

  excellent yields up to 99% and with complete chemoselectivity. The mechanism is suggested to involve cop- per(II)-mediated dehydration of the homoallylic amino alcohol. Protonation of the resultant cop- per(II)-activated aminodiene is then thought to trigger subsequent intramolecular hydroamination to give the partially hydrogenated nitrogen heterocycle.

  描述了一种新的高效合成路线，该路线依赖于温和且操作简便的条件下，三氟甲磺酸铜（II）催化均烯丙基氨基醇分子内胺化，生成反式-2,5-二氢-1 H-吡咯和1,2-二氢喹啉。对于反应导致的反式-2,5-二氢-1- ħ -吡咯产物，的52-83％的产率与沿反式选择性高达> 99：1个博士和EE值高达97％是从对映体富集完成1-（甲苯磺酰氨基）戊-4-烯-2-醇，ee范围为91–99％。不需要惰性和无湿气的条件，涉及1- [2-（甲苯磺酰基氨基）苯基] but-3-en-1-ols的反应可提供相应的1,2-二氢喹啉产物，收率高达99％，且完全的化学选择性。建议该机制涉及铜（II）介导的均烯丙基氨基醇的脱水。然后认为所得的经铜（II）活化的氨基二烯的质子化会触发随后的分子内加氢胺化反应，从而产生部分氢化的氮杂环。
• One-Pot Transition-Metal-Free Synthesis of Weinreb Amides Directly from Carboxylic Acids
  作者：Danfeng Huang、Yulai Hu、Teng Niu、Ke-Hu Wang、Changming Xu、Yingpeng Su、Ying Fu

  DOI：10.1055/s-0033-1340317

  日期：——

  directly from carboxylic acids, N,O-dimethylhydroxylamine, and phosphorus trichloride in one pot at 60 °C in toluene in high yields, thus avoiding the separation of the moisture and air sensitive intermediate P[NMe(OMe)]3 in advance. Sterically hindered carboxylic acids also give the corresponding Weinreb amides in excellent yields. Various functional groups are tolerated on the carboxylic acid. The method

  摘要 在一个锅中于60°C在甲苯中以高收率直接由羧酸，N，O-二甲基羟胺和三氯化磷直接制备Weinreb酰胺，从而避免了对水分和空气敏感的中间体P [NMe（OMe）] 3的分离。提前。受位阻的羧酸也以优异的产率得到相应的Weinreb酰胺。羧酸上具有各种官能团。该方法工艺简单，收率高，适合大规模生产。 在一个锅中于60°C在甲苯中以高收率直接由羧酸，N，O-二甲基羟胺和三氯化磷直接制备Weinreb酰胺，从而避免了对水分和空气敏感的中间体P [NMe（OMe）] 3的分离。提前。受位阻的羧酸也以优异的产率得到相应的Weinreb酰胺。羧酸上具有各种官能团。该方法工艺简单，收率高，适合大规模生产。
• Epoxy-Annulations by Reactions of α-Amido Ketones with Vinyl Sulfonium Salts. Reagent versus Substrate Control and Kinetic Resolution
  作者：Matthew G. Unthank、Bahareh Tavassoli、Varinder K. Aggarwal

  DOI：10.1021/ol800318h

  日期：2008.4.1

  Diphenyl vinyl sulfonium salt and chiral amido-ketones undergo highly diastereoselective epoxy-annulation reactions in good yield. The use of a chiral vinyl sulfonium salt dominates the stereochemical outcome of the annulation reaction (reagent control is greater than substrate control), and this has allowed the kinetic resolution of racemic amido-ketones to be achieved.

  二苯基乙烯基sulf盐和手性酰胺基酮以高收率进行高度非对映选择性的环氧环化反应。手性乙烯基sulf盐的使用在环化反应的立体化学结果中占主导地位（试剂控制大于底物控制），这使消旋酰胺基的动力学拆分成为可能。
• Studies on Instructive Construction of <i>exo</i>-Olefin Terminated Five- and Six-Membered Nitrogen Heterocycles: SmI₂-Mediated Intramolecular Cyclization of Haloalkynals
  作者：Kazunori Takahashi、Kei Fukushima、Marina Seto、Azusa Togashi、Yuichi Arai、Masayoshi Tsubuki、Toshio Honda

  DOI：10.1021/acs.joc.8b01440

  日期：2018.9.7

  pyrrolidine and piperidine frameworks was developed by employing SmI2-mediated intramolecular radical cyclization of haloalkynaks. The radical cyclization affording 2,3-disubstituted pyrrolidines and piperidines proceeded in a highly stereoselective manner. However, decreasing stereoselectivety was observed in the preparation of 2,4-disubstituted pyrrolidine and 3,4-disubstituted piperidine derivatives in the

  通过利用SmI 2介导的卤代炔烃分子内自由基环化反应，开发了外烯烃终止的吡咯烷和哌啶骨架的立体选择性结构。自由基环化得到2，3-二取代的吡咯烷和哌啶以高度立体选择性的方式进行。然而，在环化过程中，在制备2，4-二取代的吡咯烷和3，4-二取代的哌啶衍生物中观察到降低的立体选择性。
• An efficient [3+2] annulation for the asymmetric synthesis of densely-functionalized pyrrolidinones and γ-butenolides
  作者：Hui Qian、Song Sun、Wanxiang Zhao、Jianwei Sun

  DOI：10.1039/d0cc05188h

  日期：——

  [3+2] annulation of siloxy alkynes that provides robust access to highly enantioenriched, densely-substituted pyrrolidinones and γ-butenolides, whose direct synthesis remains challenging. This process also represents a rare asymmetric synthesis of enantrioenriched molecules from siloxy alkynes.

  本文公开了一种新的[3 + 2]硅烷氧基炔烃环化反应，可提供对苯二酚和γ-丁烯化物的高度对映体富集，致密取代的吡咯烷酮和它们的直接合成方法，这些化合物的直接合成仍具有挑战性。该过程还代表了从甲硅烷氧基炔烃中稀有的对映体富集分子的罕见不对称合成。