1-tosyl-pyridin-2(1H)-one | 29637-85-2

• 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: 1-tosyl-pyridin-2(1H)-one
• 英文别名: 1-(4-Methylphenyl)sulfonylpyridin-2-one
• CAS: 29637-85-2
• 化学式: C₁₂H₁₁NO₃S
• 分子量: 249.29
• InChiKey: DFLQGOSICUNNAI-UHFFFAOYSA-N

物化性质

• 熔点：
  137-138 °C(Solv: ethyl acetate (141-78-6))
• 沸点：
  410.6±38.0 °C(Predicted)
• 密度：
  1.353±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  62.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-tosyl-pyridin-2(1H)-one 以 二氯甲烷 为溶剂， 反应 21.0h， 以73%的产率得到pyridin-2-yl tosylate
  参考文献：
  名称：

  Diels-Alder cycloadditions using nucleophilic 2-pyridones. Regiocontrolled and stereocontrolled synthesis of unsaturated, bridged, bicyclic lactams

  摘要：

  Captodative 3-oxy-and 3-(tolylthio)-1-tosyl-2-pyridones 1a-1d are shown to be reactive as nucleophilic dienes undergoing 2 + 4-cycloadditions with various electrophilic alkenes under sufficiently mild thermal conditions (90-100-degrees-C) that the initial bicylic lactam adducts can be isolated on gram scale in fair to very good yields (23-83%) without loss of an isocyanate from the heteroatom bridge. These bicyclic adducts are formed with complete regiocontrol and stereocontrol. For pyridone sulfide 1d, these Diels-Alder cycloadditions are the first examples of a captodative unsaturated sulfide acting as an enophile. NMR data (C-13) are presented correlating the electron density in the pyridone diene systems with their Diels-Alder reactivity, and some transformations of the bicyclic lactam adducts are shown to illustrate the value and versatility of these richly functionalized synthetic intermediates.

  DOI：

  10.1021/jo00041a010
• 作为产物：
  描述：

  1-(4-Methylphenyl)sulfonyl-4-phenylsulfanyl-2,3-dihydropyridin-6-one 在 potassium fluoride 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 生成 1-tosyl-pyridin-2(1H)-one
  参考文献：
  名称：

  Aza-Diels-Alder反应与硫代取代的1,3-二烯与芳基磺酰基异氰酸酯的合成应用

  摘要：

  芳基磺酰基异氰酸酯与硫取代的1,3-二烯经3-环丁烯前体1的第一次氮杂-狄尔斯-阿尔德反应使环化产物3完全控制了区域选择性和化学选择性。环化产物3a和4与亲核试剂和碱进行进一步有趣的反应，得到有用的杂环化合物。

  DOI：

  10.1016/s0040-4039(00)01447-7

文献信息

• Synthesis and Applications of Tetrahydro-2-pyridinones via aza-Diels-Alder Reactions of Thio-substituted 1,3-Dienes with Arylsulfonyl Isocyanates
  作者：Shang-Shing Chou、Chia-Cheng Hung

  DOI：10.1055/s-2001-18710

  日期：——

  The first aza-Diels-Alder reactions of arylsulfonyl isocyanates with thio-substituted 1,3-dienes via the 3-sulfolene precursors 1 gave the cyclized products 3 with complete control of chemo- and regioselectivity. The cyclized products 3a and 5 underwent further reactions with nucleophiles and bases to give useful heterocyclic compounds. The N-tosyl group of the cyclic products could be selectively replaced by hydrogen or another substituent.

  芳基磺酰基异氰酸与硫取代的1,3-二烯通过3-砜基烯前体1进行的首批aza-Diels-Alder反应，完全控制了化学选择性和区域选择性地得到了环化产物3。环化产物3a和5与亲核试剂和碱进一步反应，生成了有用的杂环化合物。环状产物的N-对甲苯磺酰基可以被选择性地替换为氢或其他取代基。
• Iron‐Catalyzed Reactions of 2‐Pyridone Derivatives: 1,6‐Addition and Formal Ring Opening/Cross Coupling
  作者：Lin Huang、Yiting Gu、Alois Fürstner

  DOI：10.1002/asia.201900865

  日期：2019.11.18

  In the presence of simple iron salts, 2-pyridone derivatives react with Grignard reagents under mild conditions to give the corresponding 1,6-addition products; if the reaction medium is supplemented with an aprotic dipolar cosolvent after the actual addition step, the intermediates primarily formed succumb to ring opening, giving rise to non-thermodynamic Z,E-configured dienoic acid amide derivatives

  在简单的铁盐存在下，2-吡啶酮衍生物在温和的条件下与格氏试剂反应，生成相应的1,6-加成产物。如果在实际添加步骤之后向反应介质中添加了质子惰性的偶极助溶剂，则中间体主要形成屈服开环，从而导致非热力学的Z，E构型的二烯酰胺衍生物，否则很难制备。对照实验以及（三羰基）铁吡啶酮配合物的分离和晶体学表征表明，原位生成的活性铁催化剂对嵌入基质杂环系统中的极化二烯系统表现出高亲和力，这很可能是因为实际识别元素。
• Heteroaromatic Tosylates as Electrophiles in Regioselective Mizoroki-Heck-Coupling Reactions with Electron-Rich Olefins
  作者：Thomas M. Gøgsig、Anders T. Lindhardt、Mouloud Dekhane、Julie Grouleff、Troels Skrydstrup

  DOI：10.1002/chem.200900313

  日期：2009.6.8

  Easy and direct: Regioselective Mizoroki–Heck‐coupling reactions using heteroaromatic tosylates as electrophiles were achieved, thus providing direct and easy access to highly functionalized α‐heteroarylvinyl amides and ethers.

  简便，直接：实现了使用杂芳族甲苯磺酸盐作为亲电试剂的区域选择性Mizoroki-Heck偶联反应，从而可以直接，轻松地获得高度官能化的α-杂芳基乙烯基酰胺和醚。
• Five‐Membered Nitrogen Heterocycles Synthesis through 1,3‐Dipolar Cycloaddition of Non‐Stabilized Azomethine Ylides with 2‐Pyridone Heteroaromatic Systems as Dipolarophiles
  作者：Sami Ben Salah、Morgane Sanselme、Yves Champavier、Mohamed Othman、Adam Daïch、Isabelle Chataigner、Ata Martin Lawson

  DOI：10.1002/ejoc.202001404

  日期：2021.1.8

  3‐dipolar cycloadditions of non‐stabilized azomethine ylides with diversely substituted 2‐pyridone systems, bearing two potential C=C dipolarophilic sites was reported. The TFA‐catalyzed cycloadditions involving the in situ prepared electron‐rich 1,3‐dipole are studied according to the nature of pyridone substituents. These reactions occur in mild conditions, good yields, and show a full control of the

  据报道，一系列带有两个潜在的C = C双亲性位点的，不稳定的偶氮甲亚胺的高效1,3-偶极环加成反应，带有不同取代的2-吡啶酮体系。根据吡啶酮取代基的性质，研究了TFA催化的环加成反应，该反应涉及就地制备的富电子的1,3-偶极子。这些反应在温和的条件下发生，具有良好的收率，并显示出对区域选择性的完全控制。
• Catalytic Transformations of 2-Pyridones by Rhodium-Mediated Carbene Transfer
  作者：Jiahui Su、Qiongya Li、Ying Shao、Jiangtao Sun

  DOI：10.1021/acs.orglett.2c00151

  日期：2022.3.4

  compounds has been realized by using a chiral rhodium complex as the catalyst, and the corresponding chiral cyclopropanes could be formed in good yields with high enantioselectivities. Moreover, using acceptor–acceptor dimethyl 2-diazomalonate as the carbene precursor, a novel 1,4-rearrangement of a Boc group from N to C has also been discovered under rhodium catalysis.

  以手性铑配合物为催化剂，实现了N-取代的2-吡啶酮与重氮化合物的对映选择性环丙烷化反应，能够以良好的收率和高对映选择性生成相应的手性环丙烷。此外，使用受体-受体 2-重氮丙二酸二甲酯作为卡宾前体，还发现了在铑催化下 Boc 基团从 N 到 C 的新型 1,4-重排。