(Z)-N-benzyl-(1,2:3,4-di-O-isopropylidene-α-D-galactopyranos-6-ylidene)amine N-oxide | 191997-37-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: (Z)-N-benzyl-(1,2:3,4-di-O-isopropylidene-α-D-galactopyranos-6-ylidene)amine N-oxide
• 英文别名: (Z)-N-(6-deoxy-1,2:3,4-di-O-isopropylidene-α-D-galacto-1,5-pyranose-6-yliden)benzylamine N-oxide；N-benzyl-1-[(1S,2R,6R,8R,9S)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-8-yl]methanimine oxide
• CAS: 191997-37-2；147455-48-9
• 化学式: C₁₉H₂₅NO₆
• 分子量: 363.411
• InChiKey: ZWWHPBXOFRCBMM-LMZPHRPUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  74.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (Z)-N-benzyl-(1,2:3,4-di-O-isopropylidene-α-D-galactopyranos-6-ylidene)amine N-oxide 在 碳酸氢钠 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 24.75h， 生成 (E)-6,7-didehydro-6,7-dideoxy-1,2:3,4-di-O-isopropylidene-α-D-galacto-octodialo-1,5-pyranose
  参考文献：
  名称：

  Higher glycosamino acid precursors: C7 and C8 aminodialdoses via regio- and stereoselective [3+2] cycloaddition of vinyl trimethylsilane to C-glycosyl nitrones

  摘要：

  Protected C-7 and C-8 aminodialdoses were prepared stereoselectively from readily available C-5 and C-6 monosaccharide N-benzyl nitrones, by regio- and diastereoselective 1,3-dipolar cycloaddition reactions with vinyl trimethylsilane, followed by acetyl chloride-mediated cleavage of the 5-(trimethylsilyl)isoxazolidine formed. The cycloaddition reaction took place in moderate to good global yields (67-74%); estimation of diastereoselectivities from isolated yields showed total endo preference for the reaction of the D-galacto configured nitrone and high endo preference for the D-ribo analogue, but exo preference for the D-Xylo configured substrate. Attack on the re face of the nitrone was predominant in all cases. The absolute configuration of one of the protected 3-(alpha-D-galacto-pentopyranos-5-yl)isoxazolidine products was assigned by X-ray crystallographic analysis, allowing correlation of the configuration at the new stereogenic centre in the corresponding aminodialdose. For non-crystalline isoxazolidines, configurations were assigned on the basis of NOESY experiments and/or chemical correlation. Combined yields of aminodialdoses coming from isoxazolidines having identical configuration at C(3) sometimes reached high values (up to 90%). These compounds are precursors of higher-chain glycosamino acids. (C) 2002 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(02)00543-8
• 作为产物：
  描述：

  1,2：3,4-二-O-异亚丙基-α-D-半乳糖-己二醛-1,5-吡喃糖 、 N-苄基羟胺 在 magnesium sulfate 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以80%的产率得到(Z)-N-benzyl-(1,2:3,4-di-O-isopropylidene-α-D-galactopyranos-6-ylidene)amine N-oxide
  参考文献：
  名称：

  Synthesis of N-Benzyl Nitrones

  摘要：

  A general procedure for the synthesis of twenty-seven chiral and achiral N-benzyl nitrones 1 is described.

  DOI：

  10.1080/00397919408010565

文献信息

• A New and Expedient Diastereoselective Synthesis of α-(Hydroxyamino)phosphonates and α-Aminophosphonates by Silyl Triflate Promoted Diethyl Phosphite Addition to Chiral N-Benzyl Nitrones
  作者：Carmela De Risi、Daniela Perrone、Alessandro Dondoni、Gian Piero Pollini、Valerio Bertolasi

  DOI：10.1002/ejoc.200200698

  日期：2003.5

  efficient methodology for the synthesis of α-aminophosphonates has been developed taking advantage of the tert-butyldimethylsilyl triflate activated addition of diethyl phosphite to N-benzyl nitrones derived from chiral α-alkoxy and α-(Boc-amino) aldehydes. The stereoselective carbon− phosphorus bond-forming reaction proceeded smoothly to give α-(hydroxyamino)phosphonate intermediates as the primary

  已经开发了一种合成 α-氨基膦酸酯的有效方法，利用叔丁基二甲基甲硅烷基三氟甲磺酸酯活化亚磷酸二乙酯与衍生自手性 α-烷氧基和 α-（Boc-氨基）醛的 N-苄基硝酮的加成。立体选择性碳-磷键形成反应顺利进行，得到 α-（羟基氨基）膦酸酯中间体作为主要加合物，随后通过常规还原方法将其转化为相应的多羟基化 α-氨基-和 α,β-二氨基膦酸酯。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• Novel 6-position modified 1-thioalkyl-lincosamines
  作者：Hardwin O’Dowd、Jason G. Lewis、Mikhail F. Gordeev

  DOI：10.1016/j.tetlet.2008.02.167

  日期：2008.4

  A general method for the synthesis of 6-position modified lincosamines via stereospecific nucleophilic addition to readily available galactose 6-nitrone has been developed. A new route for the stereospecific installation of thioalkyl groups at the 1-position was also developed. These methods allow access to a variety of new derivatives of antibacterial lincosamides.

  已经开发了通过立体定向亲核加成到容易获得的半乳糖6-硝基上来合成6-位修饰的林可胺的通用方法。还开发了在1位立体定向安装硫代烷基的新方法。这些方法允许获得各种抗菌林可酰胺衍生物。
• Highly diastereoselective 1,3-dipolar cycloadditions of chiral non-racemic nitrones to 1,2-diaza-1,3-dienes: an experimental and computational investigation
  作者：Roberta Majer、Olga Konechnaya、Ignacio Delso、Tomas Tejero、Orazio A. Attanasi、Stefania Santeusanio、Pedro Merino

  DOI：10.1039/c4ob01371a

  日期：——

  Asymmetric 1,3-dipolar cycloadditions between 1,2-diaza-1,3-dienes and chiral non-racemic nitrones to give 3-substituted-5-diazenyl isoxazolidines were studied both experimentally and theoretically. Whereas cyclic nitrones provide complete selectivity for the cycloaddition reaction (only one isomer is obtained), acyclic nitrones derived from D-glyceraldehyde and D-galactose lead to 1 : 1 mixtures of

  通过实验和理论研究了1,2-二氮杂1,3-二烯与手性非外消旋硝基之间的不对称1,3-偶极环加成反应，得到3-取代的5-二氮杂异恶唑烷。环状硝酮为环加成反应提供了完全的选择性（仅获得一种异构体），而衍生自D-甘油醛和D-半乳糖的无环硝酮则形成了两种异构体的1：1混合物。基于反应性指数的DFT分析与二氮烯基的高吸电子特性相符，可以正确预测反应的区域化学。基于过渡态理论的考虑溶剂效应（PCM模型）的相同理论研究与观察到的实验结果在质量上也吻合。
• Stereoselective synthesis of 3-glycosyl-5-methoxycarbonyl-isoxazolidines from d-galactose and d-glucose
  作者：Pastora Borrachero、Francisca Cabrera-Escribano、Manuel Gómez-Guillén、Ma Isabel Torres

  DOI：10.1016/j.tetlet.2004.04.161

  日期：2004.6

  Regio- and stereoselective cycloaddition of methyl acrylate to C-glycosyl nitrones derived from d-galactose and d-glucose, giving 5-methoxycarbonyl-3-(pentoglycos-5-yl or pentitol-1-yl)isoxazolidines, is reported. Transformation of one of them into a 4-hydroxy-2-(pentoglycos-5-yl)pyrrolidine derivative, potentially useful in a route to polyhydroxy-perhydroazaazulenes, was achieved.

  据报道，丙烯酸甲酯的区域和立体选择性环加成反应衍生自d-半乳糖和d-葡萄糖的C-糖基硝酮，得到5-甲氧基羰基-3-（戊糖5-基或戊醇-1-基）异恶唑烷。实现了其中之一向4-羟基-2-（五糖基-5-基）吡咯烷衍生物的转化，该衍生物可能在制备多羟基-过氢氮杂azazulenes的途径中有用。
• Highly Diastereoselective 1,3-Dipolar Cycloaddition of a d-Galactose-Derived Nitrone with Dimethyl Maleate: Synthesis of Polyhydroxylated Perhydroaza­azulenes
  作者：Dilip Dhavale、Omprakash Bande、Vrushali Jadhav、Vedavati Puranik

  DOI：10.1055/s-0029-1217541

  日期：2009.7

  An intermolecular 1,3-dipolar cycloaddition of a d-­galactose-derived nitrone with dimethyl maleate was found to be perfectly diastereoselective at the nitrone carbon to give exclusive formation of isoxazolidine. The N-O bond reductive cleavage in isoxazolidine followed by lactam reduction afforded a pyrrolidine ring skeleton with sugar appendage that on acetonide cleavage and reductive amino-cyclization gave hitherto unknown hydroxy­methyl-substituted hexa- and pentahydroxy perhydroazaazulenes.

  研究发现，由 d-半乳糖衍生的腈酮与马来酸二甲酯进行分子间 1,3-二极环加成反应时，腈酮碳具有完全的非对映选择性，从而独家生成了异恶唑烷。异噁唑烷中的 N-O 键还原裂解后，再通过内酰胺还原，可得到带有糖附属物的吡咯烷环骨架，通过丙酮裂解和还原氨基环化，可得到迄今未知的羟甲基取代的六羟基和五羟基全氢氮杂环戊烯。