2-(4-nitrobenzyl)-1,3-dioxolane | 134485-50-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-(4-nitrobenzyl)-1,3-dioxolane
• 英文别名: 1,3-Dioxolane, 2-[(4-nitrophenyl)methyl]-；2-[(4-nitrophenyl)methyl]-1,3-dioxolane
• CAS: 134485-50-0
• 化学式: C₁₀H₁₁NO₄
• 分子量: 209.202
• InChiKey: DNFLWMOAKGVPAV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  64.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-(4-nitrobenzyl)-1,3-dioxolane 在 palladium on activated charcoal 氢气 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 7.0h， 生成 N-<4-(1,3-dioxolan-2-ylmethyl)phenyl>-N-(phenylmethyl)benzenemethanamine
  参考文献：
  名称：

  Antibody bait and switch catalysis: a survey of antigens capable of inducing abzymes with acyl-transfer properties

  摘要：

  Antibodies have been shown to catalyze acyl-transfer reactions. Various antigens have been applied to these hydrolytic reactions, but typically all encompass the same theme of incorporating a monoanionic phosphonate/phosphonamidate. To expand the scope and capabilities of these abzymes, we have directed our attention toward new strategies in antigen design. One method, which we have termed ''bait and switch'' catalysis, uses haptens to elicit amino acid(s) within the binding pocket of an antibody that can accelerate hydrolysis. We reported initial success of this methodology utilizing the cationic hapten 1 for obtaining abzymes that hydrolyzed benzoate ester 6. In addition, we showed how the structurally identical but neutral hapten 2 was unable to induce catalytic antibodies. To further identify those factors critical in the generation of hydrolytic abzymes via our bait and switch methodology, we have (1) designed and synthesized three new homologues of 1 in which we have varied the type of charge/no charge and its location, (2) screened and identified catalytic antibodies from these antigens, (3) determined affinity constants of a number of these monoclonal antibodies (catalytic and noncatalytic) for their respective haptens and possible substrates (ester/amide), (4) performed steady-state kinetics, inducing a pH-rate profile on one of these abzymes, and (5) used chemical modifying reagents to identify which amino acid residue(s) are involved in these catalytic processes.

  DOI：

  10.1021/ja00014a039
• 作为产物：
  描述：

  4-硝基苯乙烯 在 lead(IV) acetate 、 calcium sulfate 、 Rexyn 101 (H) cation-exchange resin 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 27.0h， 生成 2-(4-nitrobenzyl)-1,3-dioxolane
  参考文献：
  名称：

  Antibody bait and switch catalysis: a survey of antigens capable of inducing abzymes with acyl-transfer properties

  摘要：

  Antibodies have been shown to catalyze acyl-transfer reactions. Various antigens have been applied to these hydrolytic reactions, but typically all encompass the same theme of incorporating a monoanionic phosphonate/phosphonamidate. To expand the scope and capabilities of these abzymes, we have directed our attention toward new strategies in antigen design. One method, which we have termed ''bait and switch'' catalysis, uses haptens to elicit amino acid(s) within the binding pocket of an antibody that can accelerate hydrolysis. We reported initial success of this methodology utilizing the cationic hapten 1 for obtaining abzymes that hydrolyzed benzoate ester 6. In addition, we showed how the structurally identical but neutral hapten 2 was unable to induce catalytic antibodies. To further identify those factors critical in the generation of hydrolytic abzymes via our bait and switch methodology, we have (1) designed and synthesized three new homologues of 1 in which we have varied the type of charge/no charge and its location, (2) screened and identified catalytic antibodies from these antigens, (3) determined affinity constants of a number of these monoclonal antibodies (catalytic and noncatalytic) for their respective haptens and possible substrates (ester/amide), (4) performed steady-state kinetics, inducing a pH-rate profile on one of these abzymes, and (5) used chemical modifying reagents to identify which amino acid residue(s) are involved in these catalytic processes.

  DOI：

  10.1021/ja00014a039

文献信息

• Direct Synthesis of Protected Arylacetaldehydes by Palladium-Tetra­phosphine-Catalyzed Arylation of Ethyleneglycol Vinylether
  作者：Henri Doucet、Maurice Santelli、Isabelle Kondolff

  DOI：10.1055/s-2004-829063

  日期：——

  Through the use of [PdCl(C3H5)]2/cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl) cyclopentane as a catalyst, a range of aryl bromides undergo Heck reaction with ethyleneglycol vinylether to give regioselectively protected arylacetaldehydes in good yields. The β-arylation products were obtained in the range 93-98% selectivity with electron-poor aryl bromides. Furthermore, this catalyst can be used at low loading, even for reactions of sterically hindered aryl bromides. The arylvinyl ethers intermediates undergo subsequent ketalization to give the corresponding 2-benzyl-1,3-dioxolane derivatives.

  通过使用[PdCl(C3H5)]2/cis,cis,cis-1,2,3,4-四（二苯基膦甲基）环戊烷作为催化剂，一系列溴苯类化合物在 Heck 反应中与乙二醇乙烯醚反应，以良好的产率得到区域选择性保护的芳基乙醛。β-芳基化产物在电子贫乏的溴苯类化合物中获得了93-98%的选择性。此外，该催化剂在低负载下也可使用，甚至适用于空间位阻的溴苯类化合物的反应。芳基乙烯醚中间体随后经历缩酮化反应，得到相应的2-苄基-1,3-二氧戊环衍生物。
• Direct Synthesis of Protected Arylacetaldehydes by Tetrakis(phosphane)palladium-Catalyzed Arylation of Ethyleneglycol Vinyl Ether
  作者：Isabelle Kondolff、Henri Doucet、Maurice Santelli

  DOI：10.1002/ejoc.200500540

  日期：2006.2

  A range of aryl bromides undergo Heck reaction with ethylene glycol vinyl ether, in the presence of [PdCl(C3H5)]2/cis,cis,cis-1,2,3,4-tetrakis[(diphenylphosphanyl)methyl]cyclopentane as catalyst, to give regioselectively protected arylacetaldehydes in good yields. The β-arylation products were obtained in with 93–100 % selectivity with electron-poor aryl bromides or heteroaryl bromides. Furthermore

  在[PdCl(C3H5)]2/cis,cis,cis-1,2,3,4-四[​​(二苯基膦基)甲基]环戊烷作为催化剂存在下，一系列芳基溴化物与乙二醇乙烯基醚发生Heck反应，以良好的产率得到区域选择性保护的芳基乙醛。用缺电子的芳基溴化物或杂芳基溴化物以 93-100% 的选择性获得 β-芳基化产物。此外，该催化剂可以在低负载下使用，甚至用于与位阻芳基溴化物的反应。芳基乙烯基醚中间体经过随后的缩酮化得到相应的 2-苄基-1,3-二氧戊环衍生物。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
• Molecules with antibody combining sites that catalyze hydrolysis
  申请人：Scripps Clinic and Research Foundation

  公开号：US05187086A1

  公开（公告）日：1993-02-16

  An antibody molecule or molecule containing antibody combining site portions (catalytic molecule) that catalytically hydrolyzes a preselected carboxylic acid amide or ester bond of a reactant ligand, methods of making and using the catalytic molecule, and cells that produce those molecules are disclosed. The catalytic molecules bind to a reactant ligand containing the bond to be hydrolyzed and also to a haptenic ligand. The haptenic ligand is structurally analogous to the reactant ligand and contains a tetrahedral carbon atom that is bonded to a hydroxyl group and to a saturated carbon atom at a position in the haptenic ligand that corresponds to position of the carbonyl group and its bonded heteroatom of the reactant ligand. The haptenic ligand also contains a group that bears an ionic charge in aqueous solution at physiological pH values that is not present at a corresponding position of the reactant ligand. The ionic charge-bearing group is located in the hapten within 7 .ANG.ngstroms of the tetrahedral carbon atom.

  本文介绍了一种抗体分子或含有抗体结合位点部分（催化分子），该催化分子具有催化水解反应配体的预选羧酸酰胺或酯键的能力，以及制备和使用该催化分子的方法和产生这些分子的细胞。催化分子结合到含有要水解的键的反应配体上，并且还结合到一个半抗原配体上。半抗原配体在结构上类似于反应配体，并且在半抗原配体中，一个四面体碳原子与一个羟基和一个饱和碳原子键合，该四面体碳原子的位置对应于反应配体的羰基团和其键合杂原子的位置。半抗原配体还包含一个在生理pH值下在水溶液中带有离子电荷的基团，该离子电荷基团在反应配体的相应位置上不存在。该带电基团在半抗原内距离四面体碳原子小于7埃。
• Catalyst-free site-selective cross-aldol bioconjugations
  作者：Nicholas D. J. Yates、Saeed Akkad、Amanda Noble、Tessa Keenan、Natasha E. Hatton、Nathalie Signoret、Martin A. Fascione

  DOI：10.1039/d2gc02292c

  日期：——

  We present catalyst-free “green” site-selective protein bioconjugations that utilise aldol condensations and are compatible with click chemistries, and construct a nanobody-derived bioconjugate capable of selectively labelling prostate cancer cells.

  我们提出了无催化剂的“绿色”位点选择性蛋白质生物共轭反应，利用了醛缩反应，并且与点击化学反应兼容，并构建了一种纳米体来源的生物共轭物，能够选择性地标记前列腺癌细胞。
• Synthesis of functionalised isochromans: epoxides as aldehyde surrogates in hexafluoroisopropanol
  作者：Cyprien Muller、Filip Horký、Marie Vayer、Andrei Golushko、David Lebœuf、Joseph Moran

  DOI：10.1039/d2sc06692k

  日期：——

  pot by subsequent ring-opening, reductions, and intra- and intermolecular Friedel–Crafts reactions, also in HFIP. Finally, owing to the high pharmacological relevance of the isochroman motif, the synthesis of drug analogues was demonstrated.

  oxa-Pictet-Spengler 反应可以说是构建优先等色满基序最直接和模块化的方法，但其范围主要限于苯甲醛衍生物和沿脂肪链缺乏取代的富电子 β-苯基乙醇。在这里，我们描述了这种反应的一种变体，它从环氧化物而不是醛开始，大大扩展了反应的范围和速率（<1 小时，20 °C）。除了促进最初的 Meinwald 重排外，使用六氟异丙醇 (HFIP) 作为溶剂还扩大了亲电试剂范围，包括相当于酮、脂肪醛和苯乙酰醛的伙伴，以及包括适度电子失活和高度取代的 β-苯基乙醇的亲核试剂范围. 通过随后的开环、还原以及分子内和分子间 Friedel-Crafts 反应，在 HFIP 中，产品可以很容易地在同一锅中进一步衍生化。最后，由于等色满基序的高度药理学相关性，证明了药物类似物的合成。