通过分子内环化/甲基化一步合成螺吡唑啉
One Pot Spiropyrazoline Synthesis via Intramolecular Cyclization/Methylation.
作者信息
Dadiboyena Sureshbabu, Hamme Ashton T
机构信息
Department of Chemistry & Biochemistry, College of Science, Engineering and Technology, Jackson State University, Jackson, Mississippi 39217 USA.
出版信息
Tetrahedron Lett. 2011 May 18;52(20):2536-2539. doi: 10.1016/j.tetlet.2011.03.004.
Abstract
Regioisomeric spiropyrazolines were synthesized through a tandem intramolecular cyclization/methylation reaction of a functionalized 5,5-disubstituted pyrazoline in one reaction vessel. The 5,5-pyrazolines were constructed through a 1,3-dipolar cycloaddition reaction of aromatic ring containing nitrile imines and a disubstituted geminal alkene. An evaluation of the relative location of the nucleophilic and electrophilic functional groups on the pyrazoline was performed in order to ascertain the best pyrazoline system for the intramolecular cyclization/methylation reaction. Higher spiropyrazoline isolated yields were realized from pyrazolines with the electrophilic ester located further away from the pyrazoline when compared to pyrazolines with a directly bonded ester.
摘要
通过在一个反应容器中使功能化的5,5-二取代吡唑啉进行串联分子内环化/甲基化反应，合成了区域异构体螺吡唑啉。5,5-吡唑啉是通过含腈亚胺的芳香环与二取代偕二烯烃的1,3-偶极环加成反应构建的。对吡唑啉上亲核和亲电官能团的相对位置进行了评估，以确定用于分子内环化/甲基化反应的最佳吡唑啉体系。与具有直接键合酯的吡唑啉相比，亲电酯离吡唑啉更远的吡唑啉实现了更高的螺吡唑啉分离产率。
相似文献
1
One Pot Spiropyrazoline Synthesis via Intramolecular Cyclization/Methylation.
Tetrahedron Lett. 2011 May 18;52(20):2536-2539. doi: 10.1016/j.tetlet.2011.03.004.
2
Construction of Novel Spiroisoxazolines via Intramolecular Cyclization/Methylation.
Tetrahedron Lett. 2009 Sep 30;50(39):5516-5519. doi: 10.1016/j.tetlet.2009.07.095.
3
Pyrazoline and Analogs: Substrate-based Synthetic Strategies.
Curr Org Synth. 2024;21(7):823-836. doi: 10.2174/1570179421666230822100043.
4
Substrate-Switched Chemodivergent Pyrazole and Pyrazoline Synthesis: [3 + 2] Cycloaddition/Ring-Opening Rearrangement Reaction of Azadienes with Nitrile Imines.
J Org Chem. 2022 Mar 4;87(5):3389-3401. doi: 10.1021/acs.joc.1c02998. Epub 2022 Feb 14.
5
[3 + 2] Cycloaddition of Nitrile Imines with Enamides: An Approach to Functionalized Pyrazolines and Pyrazoles.
J Org Chem. 2021 Jan 1;86(1):559-573. doi: 10.1021/acs.joc.0c02244. Epub 2020 Dec 10.
6
5-(Methylthio)tetrazoles as Versatile Synthons in the Stereoselective Synthesis of Polycyclic Pyrazolines via Photoinduced Intramolecular Nitrile Imine-Alkene 1,3-Dipolar Cycloaddition.
Chem Sci. 2014 Jun 1;5(6):2407-2415. doi: 10.1039/C4SC00107A.
7
Regioselective Cycloaddition of Nitrile Imines to 5-Methylidene-3-phenyl-hydantoin: Synthesis and DFT Calculations.
Int J Mol Sci. 2023 Jan 9;24(2):1289. doi: 10.3390/ijms24021289.
8
Highly enantioselective catalytic 1,3-dipolar cycloadditions of α-alkyl diazoacetates: efficient synthesis of functionalized 2-pyrazolines.
Org Biomol Chem. 2015 Mar 7;13(9):2745-9. doi: 10.1039/c4ob02372b.
9
Synthesis of oxindolyl pyrazolines and 3-amino oxindole building blocks via a nitrile imine [3 + 2] cycloaddition strategy.
Org Lett. 2012 Oct 19;14(20):5266-9. doi: 10.1021/ol302425h. Epub 2012 Oct 10.
10
Green synthesis of novel spiropyrazoline-indolinones in neutral deep eutectic solvents and DFT studies.
Heliyon. 2023 Dec 20;10(1):e23814. doi: 10.1016/j.heliyon.2023.e23814. eCollection 2024 Jan 15.
引用本文的文献
1
Green synthesis of novel spiropyrazoline-indolinones in neutral deep eutectic solvents and DFT studies.
Heliyon. 2023 Dec 20;10(1):e23814. doi: 10.1016/j.heliyon.2023.e23814. eCollection 2024 Jan 15.
2
Prescribed drugs containing nitrogen heterocycles: an overview.
RSC Adv. 2020 Dec 15;10(72):44247-44311. doi: 10.1039/d0ra09198g. eCollection 2020 Dec 9.
3
A Molecular Electron Density Theory Study of the Synthesis of Spirobipyrazolines through the Domino Reaction of Nitrilimines with Allenoates.
Molecules. 2019 Nov 16;24(22):4159. doi: 10.3390/molecules24224159.
4
Diversity oriented synthesis and IKK inhibition of aminobenzimidazole tethered quinazoline-2,4-diones, thioxoquinazolin-4-ones, benzodiazepine-2,3,5-triones, isoxazoles and isoxazolines.
Bioorg Med Chem Lett. 2015 Feb 1;25(3):685-9. doi: 10.1016/j.bmcl.2014.11.078. Epub 2014 Dec 8.
5
Gold Nanopopcorn Attached Single-Walled Carbon Nanotube Hybrid for Rapid Detection and Killing of Bacteria.
J Mater Chem B. 2014;2(43):7534-7543. doi: 10.1039/C4TB01195C.
6
Synthesis and Tautomerism of Spiro-Pyrazolines.
Tetrahedron Lett. 2014 Apr 2;55(14):2208-2211. doi: 10.1016/j.tetlet.2014.02.052.
7
Environmentally Benign Lewis Acid Promoted [2+3]-Dipolar Cycloaddition Reactions of Nitrile Imines with Alkenes in Water.
European J Org Chem. 2013 Nov;2013(33):7567-7574. doi: 10.1002/ejoc.201300840.
8
Solid Phase Synthesis of Isoxazole and Isoxazoline-carboxamides via [2+3]-Dipolar Cycloaddition Using Resin-bound Alkynes or Alkenes.
Tetrahedron Lett. 2012 Apr 18;53(16):2096-2099. doi: 10.1016/j.tetlet.2012.02.041.
本文引用的文献
1
Cycloaddition reactions of allenylphosphonates and related allenes with dialkyl acetylenedicarboxylates, 1,3-diphenylisobenzofuran, and anthracene.
J Org Chem. 2011 Feb 4;76(3):920-38. doi: 10.1021/jo102240u. Epub 2011 Jan 10.
2
Facile Route to Tetrasubstituted Pyrazoles Utilizing Ceric Ammonium Nitrate.
Synlett. 2009(9):1490-1494. doi: 10.1055/s-0029-1217163.
3
Recent methodologies toward the synthesis of valdecoxib: a potential 3,4-diarylisoxazolyl COX-II inhibitor.
Eur J Med Chem. 2010 Nov;45(11):4697-707. doi: 10.1016/j.ejmech.2010.07.045. Epub 2010 Aug 6.
4
An alkynyliodide cycloaddition strategy for the construction of iodoisoxazoles.
J Org Chem. 2010 Aug 6;75(15):5414-6. doi: 10.1021/jo1011174.
5
Synthesis of Novel Pyrazoles via [2+3]-Dipolar Cycloaddition Using Alkyne Surrogates.
Tetrahedron Lett. 2010 Mar 3;51(9):1341. doi: 10.1016/j.tetlet.2010.01.017.
6
Construction of Novel Spiroisoxazolines via Intramolecular Cyclization/Methylation.
Tetrahedron Lett. 2009 Sep 30;50(39):5516-5519. doi: 10.1016/j.tetlet.2009.07.095.
7
A Novel Synthesis of 1,3,5-Trisubstituted Pyrazoles through a Spiro-pyrazoline Intermediate via a Tandem 1,3-Dipolar Cycloaddition/Elimination.
Tetrahedron Lett. 2009 Jan 21;50(3):291. doi: 10.1016/j.tetlet.2008.10.145.
8
Alkyne [3 + 2] cycloadditions of iodosydnones toward functionalized 1,3,5-trisubstituted pyrazoles.
J Org Chem. 2010 Feb 5;75(3):984-7. doi: 10.1021/jo902514v.
9
3,5-Isoxazoles from alpha-bromo-pentafluorophenyl vinylsulfonates: synthesis of sulfonates and sulfonamides.
Org Biomol Chem. 2009 Nov 7;7(21):4349-51. doi: 10.1039/b911098d. Epub 2009 Aug 25.
10
Investigation of the scope and regiochemistry of alkynylboronate cycloadditions with sydnones.
J Am Chem Soc. 2009 Jun 10;131(22):7762-9. doi: 10.1021/ja902460n.
Zotero 插件