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Computational and Experimental Investigation of the Diels−Alder Cycloadditions of 4-Chloro-2(H)-pyran-2-one†

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Department of Chemistry, King's College, Strand, London WC2R 2LS, UK
Cite this: J. Org. Chem. 2003, 68, 19, 7158–7166
Publication Date (Web):August 27, 2003
https://doi.org/10.1021/jo0348827
Copyright © 2003 American Chemical Society
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Abstract

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4-Chloro-2(H)-pyran-2-one undergoes thermal Diels−Alder cycloaddition with electron-deficient dienophiles to afford, without any significant selectivity, 6-endo- and 5-endo-substituted bicyclic lactone cycloadducts. In contrast to 3- and 5-bromo-2(H)-pyran-2-one, 4-chloro-2(H)-pyran-2-one does not undergo thermal cycloadditions with electron-rich dienophiles. The regio- and stereochemical preferences of the cycloadditions of 4-chloro-2(H)-pyran-2-one and other related 2(H)-pyran-2-ones are investigated computationally. Calculations were carried out on the transition states leading to the four possible regio- and stereoisomeric cycloadducts using density functional theory (B3LYP/6-31G*). These studies allow prediction of the regio- and stereoselectivity in these reactions which are in line with experimental observations.

†

 Dedicated to Prof. Gary H. Posner on the occasion of his 60th birthday.

*

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

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Coordinates of all transition states in pdb format. Absolute energies of all transition states. This material is available free of charge via the Internet at http://pubs.acs.org.

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Cited By

This article is cited by 23 publications.

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  2. Kamyar Afarinkia,, Akmal Bahar,, Michael J. Bearpark,, Yésica Garcia-Ramos,, Andrea Ruggiero,, Judi Neuss, and, Maushami Vyas. Investigation of the Diels−Alder Cycloadditions of 2(H)-1,4-Oxazin-2-ones. The Journal of Organic Chemistry 2005, 70 (23) , 9529-9537. https://doi.org/10.1021/jo051646i
  3. Kamyar Afarinkia,, Michael J. Bearpark, and, Alexis Ndibwami. An Experimental and Computational Investigation of the Diels−Alder Cycloadditions of Halogen-Substituted 2(H)-Pyran-2-ones. The Journal of Organic Chemistry 2005, 70 (4) , 1122-1133. https://doi.org/10.1021/jo048213k
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  7. Pei Gan, Myles W. Smith, Nathaniel R. Braffman, Scott A. Snyder. Pyrone Diels-Alder Routes to Indolines and Hydroindolines: Syntheses of Gracilamine, Mesembrine, and Δ 7 -Mesembrenone. Angewandte Chemie 2016, 128 (11) , 3689-3694. https://doi.org/10.1002/ange.201510520
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  9. Adil I. Khatri, Shriniwas D. Samant. Unusual tandem sequence of oxa Diels–Alder reaction, retro Diels–Alder reaction, and oxa 6π-electrocyclic ring opening in the reaction of 6-amino-4-(4-methoxyphenyl)-2H-pyran-2-ones with benzaldehydes. RSC Advances 2015, 5 (3) , 2009-2012. https://doi.org/10.1039/C4RA13374A
  10. Ariel M. Sarotti, Rolando A. Spanevello, Alejandra G. Suárez. Assessing the halogen effect in Diels–Alder reactions involving chiral α-halo enones. A combined experimental and DFT computational approach. Tetrahedron Letters 2011, 52 (32) , 4145-4148. https://doi.org/10.1016/j.tetlet.2011.05.143
  11. Wanqing Wu, Long Min, Lizhi Zhu, Chi-Sing Lee. A New Class of Enantioselective Catalytic 2-Pyrone Diels-Alder Cycloadditions. Advanced Synthesis & Catalysis 2011, 353 (7) , 1135-1145. https://doi.org/10.1002/adsc.201000927
  12. Thomas J. Gregson, John M. Herbert, Eleanor C. Row. Synthetic approaches to regiospecifically mono- and dilabelled arenes. Journal of Labelled Compounds and Radiopharmaceuticals 2011, 54 (1) , 1-32. https://doi.org/10.1002/jlcr.1783
  13. Bogdan Štefane, Andrej Perdih, Andrej Pevec, Tomaž Šolmajer, Marijan Kočevar. The Participation of 2H-Pyran-2-ones in [4+2] Cycloadditions: An Experimental and Computational Study. European Journal of Organic Chemistry 2010, 2010 (30) , 5870-5883. https://doi.org/10.1002/ejoc.201000236
  14. Wanqing Wu, Shuzhong He, Xiongfei Zhou, Chi-Sing Lee. Diels-Alder Cycloadditions of 5-Hydroxy-2-pyrones: 2H-Pyran-2,5-diones and 5-(tert-Butyldimethylsilyloxy)-2-pyrones as Synthons. European Journal of Organic Chemistry 2010, 2010 (6) , 1124-1133. https://doi.org/10.1002/ejoc.200901040
  15. James D. Kirkham, Patrick M. Delaney, George J. Ellames, Eleanor C. Row, Joseph P. A. Harrity. An alkynylboronate cycloaddition strategy to functionalised benzyne derivatives. Chemical Communications 2010, 46 (28) , 5154. https://doi.org/10.1039/c0cc01345e
  16. Atul Goel, Vishnu J. Ram. Natural and synthetic 2H-pyran-2-ones and their versatility in organic synthesis. Tetrahedron 2009, 65 (38) , 7865-7913. https://doi.org/10.1016/j.tet.2009.06.031
  17. Susan M. Larkin, Thom Vreven, Michael J. Bearpark, Keiji Morokuma. The application of the ONIOM hybrid method to the cycloaddition reactions of bromo-substituted 2( H )-pyran-2-ones. Canadian Journal of Chemistry 2009, 87 (7) , 872-879. https://doi.org/10.1139/V09-027
  18. A.J. Phillips, J.A. Henderson, K.L. Jackson. Pyrans and their Benzo Derivatives: Structure and Reactivity. 2008,,, 337-418. https://doi.org/10.1016/B978-008044992-0.00607-6
  19. Ian J. S. Fairlamb, Ciara T. O'Brien, Zhenyang Lin, King Chung Lam. Regioselectivity in the Sonogashira coupling of 4,6-dichloro-2-pyrone. Organic & Biomolecular Chemistry 2006, 4 (7) , 1213. https://doi.org/10.1039/b518232h
  20. Fraser F. Fleming, Zhiyu Zhang. Cyclic nitriles: tactical advantages in synthesis. Tetrahedron 2005, 61 (4) , 747-789. https://doi.org/10.1016/j.tet.2004.11.012
  21. Krištof Kranjc, Marijan Kočevar. Diels–Alder reaction of highly substituted 2H-pyran-2-ones with alkynes: reactivity and regioselectivity. New Journal of Chemistry 2005, 29 (8) , 1027. https://doi.org/10.1039/b504852d
  22. Kamyar Afarinkia, Akmal Bahar, Judi Neuss, Maushami Vyas. Control of electron demand in the cycloadditions of 2(H)-1,4-oxazin-2-ones. Tetrahedron Letters 2004, 45 (38) , 7121-7124. https://doi.org/10.1016/j.tetlet.2004.07.105
  23. Shingo Kiri, Yuka Odo, Huda Izzat Omar, Tetsuro Shimo, Kenichi Somekawa. Origin of the Endo/Exo Stereoselectivity and Syn/Anti Face-Selectivity in Diels–Alder Reactions, Determined by Transition State Energy Partitioning. Bulletin of the Chemical Society of Japan 2004, 77 (8) , 1499-1504. https://doi.org/10.1246/bcsj.77.1499

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