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The synthetic potential of pyridinium salt photochemistry

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Abstract

The discovery in the 1970s by Kaplan, Wilzbach and Pavlik that pyridinium salts undergo a unique cyclization reaction to produce bicyclic-aziridines was virtually unrecognized for nearly three decades. It was only comparatively recently that the process was explored in more detail and its synthetic potential exploited. In this Perspective, photocyclization reactions of pyridinium salts will be discussed, starting with the initial discovery, covering related processes of pyrylium salts, and extending to applications to the synthesis of natural and non-natural products of biomedical interest.

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References

  1. CRC Handbook of Organic Photochemistry and Photobiology, ed. W. Horspool, F. Lenci, CRC Press, 2004.

    Google Scholar 

  2. G. Desimoni, G. Tacconi, A. Barco and G. P. Pollini, in Natural Product Synthesis Through pericyclic Reactions, ACS Monograph 180, 1983, ch. 3, pp. 33–87.

    Google Scholar 

  3. E. J. Corey, S. Nozoe, Total Synthesis of α-Caryophyllene Alcohol, J. Am. Chem. Soc., 1964, 86, 1652–1653.

    Article  CAS  Google Scholar 

  4. L. Kaplan, J. W. Pavlik, K. E. Wilzbach, Photohydration of Pyridinium Ions, J. Am. Chem. Soc., 1972, 94, 3283–3284.

    Article  CAS  Google Scholar 

  5. U. C. Yoon, S. L. Quillen, P. S. Mariano, R. Swanson, J. L. Stavinoha, E. Bay, Exploratory and Mechanistic Aspects of the Electron-Transfer Photochemistry of Olefin-N-Heteroaromatic Cation Systems, J. Am. Chem. Soc., 1983, 105, 1204–1218.

    Article  CAS  Google Scholar 

  6. D. Bryce-Smith, A. Gillbert, The Organic Photochemistry of Benzene, Tetrahedron, 1976, 32, 1309–1326.

    Article  CAS  Google Scholar 

  7. K. E. Wilzbach, L. Kaplan, Photoisomerization of Dialklbenzenes, J. Am. Chem. Soc., 1964, 86, 2307–2308.

    Article  CAS  Google Scholar 

  8. J. M. Blair, D. Bryce-Smith, The Photoisomerization of Benzene to Fulvene, Proc. Chem. Soc., 1957, 287–288.

    Google Scholar 

  9. L. Kaplan, D. J. Rausch, K. E. Wilzbach, Photosolvation of Benzene, J. Am. Chem. Soc., 1972, 94, 8638–8640.

    Article  CAS  Google Scholar 

  10. S. Kato, A Theoretical Study on the Mechanism of Internal Conversion Of S1 Benzene, J. Chem. Phys., 1988, 88, 3045–3056.

    Article  CAS  Google Scholar 

  11. A. L. Sobolewski, W. Domcke, Photophysically Relevant Potential Energy Functions of Low-Lying Singlet States of Benzene, Pyridine and Pyrazine: An ab initio Study, Chem. Phys. Lett., 1991, 180, 381–386.

    Article  CAS  Google Scholar 

  12. D. P. Kjell, R. S. Sheridan, Diazabenzosemibullvalene. A Precursor to the Benzoprefulvene Biradical and Indenylmethylene, J. Am. Chem. Soc., 1986, 108, 4111–4114.

    Article  CAS  Google Scholar 

  13. L. Kaplan, K. E. Wilzbach, W. G. Brown, S. S. Yang, Phototransposition of Carbon Atoms in the Benzene Ring, J. Am. Chem. Soc., 1965, 87, 675.

    Article  CAS  Google Scholar 

  14. J. A. Barltrop, K. Dawes, A. C. Day, A. J. H. Summers, Photohydrolysis of 2,4,6-Trimethylpyrylium Perchlorate: Evidence for Isomerization to an Oxoniabenzvalene Intermediate, Chem. J. Chem. Soc. Commun., 1972, 22, 1240–1241.

    Article  Google Scholar 

  15. J. A. Barltrop, K. Dawes, A. C. Day, S. J. Nuttall, A. J. H. Summers, Light-Induced 1,2-Transposition and 2,6-Bonding in 4-Ethyl-2,6-Dimethylpyrylium Perchlorate, J. Chem. Soc,. Chem. Commun, 1973, 12, 410–411.

    Article  Google Scholar 

  16. J. A. Barltrop, K. Dawes, A. C. Day, A. J. H. Summers, Photochemistry of 4- tert-Butyl-2,6-dimethylpyrylium Perchlorate. Evidence for an Oxoniabenzvalene Intermediate, J. Am. Chem. Soc., 1973, 95, 2406–2408.

    Article  CAS  Google Scholar 

  17. J. W. Pavlik, E. L. Clennan, Photochemical Rearrangements of Pyrylium Cations, J. Am. Chem. Soc., 1973, 95, 1697–1699.

    Article  CAS  Google Scholar 

  18. J. W. Pavlik, J. Kwong, Photochemical Rearrangements of Neutral and Protonated 4-Pyrones, J. Am. Chem. Soc., 1973, 95, 7914–7916.

    Article  CAS  Google Scholar 

  19. J. W. Pavlik, L. T. Pauliukonis, Photoisomerization of 4-Pyrones. Nucleophilic Trapping of Reactive Intermediates, Tetrahedron Lett., 1976, 23, 1939–1942.

    Article  Google Scholar 

  20. J. W. Pavlik, A. P. Spada, T. E. Snead, Photochemistry of 4-Hydroxypyrylium Cations in Aqueous Sulfuric Acid, J. Org. Chem., 1985, 50, 3046–3050.

    Article  CAS  Google Scholar 

  21. R. F. Childs, M. Sakai, S. Winstein, The Observation and Behavior of the Pentamethylcyclopentadienylmethyl Cation., J. Am. Chem. Soc., 1968, 90, 7144–7146.

    Article  CAS  Google Scholar 

  22. J. D. Bene, H. H. Jaffe, Use of the CNDO Method in Spectroscopy. III. Monosubstituted Benzenes and Pyridines, J. Chem. Phys., 1968, 49, 1221–1229.

    Article  Google Scholar 

  23. R. A. King, H. P. Luthi, H. F. Schaefer, III, F. Glarner, U. Burger, The Photohydration of N-Alkylpyridinium Salts: Thoery and Experiment, Chem.–Eur. J., 2001, 7, 1734–1742.

    Article  PubMed  CAS  Google Scholar 

  24. R. F. Childs, S. Winstein, Ring Opening and Fivefold Degenerate Scrambling in Hexa- and Heptamethylbicyclo[3.1.0]hexenyl Cations, J. Am. Chem. Soc., 1968, 90, 7146–7147.

    Article  CAS  Google Scholar 

  25. E. F. Ullman, Photochemical Valence Tautomerization of 2,4,6-Triphenylpyrylium 3-oxide, J. Am. Chem. Soc., 1963, 85, 3529–3530.

    Article  CAS  Google Scholar 

  26. A. R. Katritzky, H. Wilde, Photochemically Induced Valence Bond Tautomerism and Dimerization of 3-Oxido-1-Phenylpyridinium, J. Chem. Soc., Chem. Commun., 1975, 770–771.

    Google Scholar 

  27. N. Dennis, A. R. Katritzky, H. Wilde, 1,3-Dipolar of Six-Membered Aromatic Rings. Part XXVII. Photochemically Induced Valence Bond Tautomerism and Dimerization of 3-Oxido-1-phenylpyridinium, J. Chem. Soc., Perkin I, 1976, 2338–2343.

    Google Scholar 

  28. P. E. Hansen, K. Undheim, N-Quaternary Compounds. Part XI. Syntheses of 1a,6a-Dihydroindeno[1,2-b]azirin-6(1 H)-ones and Isomerization to Isoquinolinium Derivatives, J. Chem. Soc., Perkin I, 1975, 305–308.

    Google Scholar 

  29. J. W. Lown, K. Matsumoto, Thermally Disallowed Valence Tautomerization of an Indano[1,2- b]aziridine to an Isoquinolinium Imine, J. Org. Chem., 1971, 36, 1405–1413.

    Article  CAS  Google Scholar 

  30. M. Hanaoka, C. Mukai, K. Nagami, K. Okajima, S. Yasuda, Chemical Transformation of Photoberberines. V. Photochemical Valence Isomerization of Berberinephenolbetaines to 8,14-Cycloberbines, Versatile Aziridine Derivatives for a Novel and Efficient Entry to Spirobenzylisoquinolines and Benzindenoazepines, Chem. Pharm. Bull., 1984, 32, 2230–2240.

    Article  Google Scholar 

  31. R. Ling, M. Yoshida, P. S. Mariano, Exploratory Investigations Probing a Preparatively Versatile, Pyridinium Salt Photoelectrocyclization-Solvolytic Aziridine Ring Opening Sequence, J. Org. Chem., 1996, 61, 4439–4449.

    Article  PubMed  CAS  Google Scholar 

  32. E. A. Acar, F. Glarner, U. Burger, Aminocyclopentitols from N-Alkylpyridinium Salts: A Photochemical Approach, Helv. Chim. Acta, 1998, 81, 1095–1104.

    Article  CAS  Google Scholar 

  33. C. S. Penkett, I. D. Simpson, New Methods of Preparing Cyclopentenone Ketals: The Photosolvolysis of 3-Alkoxypyridinium Tetrafluoroborates, Synlett., 1999, 1, 93–95.

    Article  Google Scholar 

  34. C. S. Penkett, I. D. Simpson, Photosolvolysis of 3-Alkoxypyridinium Tetrafluoroborates, Tetrahedron, 1999, 55, 6183–6204.

    Article  CAS  Google Scholar 

  35. Z. Zhao, E. Duesler, C. Wang, H. Guo, P. S. Mariano, Photocyclization Reactions of Cyclohexa- and Cyclopenta-Fused Pyridinium Salts. Factors Governing Regioselectivity, J. Org. Chem., 2005, 70, 8508–8512.

    Article  PubMed  CAS  Google Scholar 

  36. C. S. Penkett, I. D. Simpson, The Stereoselective Addition of Organocuprates to Cyclopentenyl Aziridine Derivatives, Tetrahedron Lett., 2001, 42, 1179–1181.

    Article  CAS  Google Scholar 

  37. F. Glarner, B. Acar, I. Etter, T. Damiano, E. A. Acar, G. Bernardinelli, U. Burger, The Photohydration of N-Glycosylpyridinium Salts and of Related Pyridinium N,O-Acetals, Tetrahedron, 2000, 56, 4311–4316.

    Article  CAS  Google Scholar 

  38. X. Feng, E. N. Duesler, P. S. Mariano, Pyridinium Salt Photochemistry in a Concise Route for Synthesis of the Trehazolin Aminocyclitol, Trehazolamine, J. Org. Chem., 2005, 70, 5618–5623.

    Article  PubMed  CAS  Google Scholar 

  39. R. Ling, P. S. Mariano, A Demonstration of the Synthetic Potential of Pyridinium Salt Photochemistry by its Application to a Stereocontrolled Synthesis of (+)−Mannostatin A, J. Org. Chem., 1998, 63, 6072–6076.

    Article  PubMed  CAS  Google Scholar 

  40. B. M. Brost, T. S. Scanlan, Synthesis of Allyl Sulfides Via a Palladium Mediated Allylation, Tetrahedron Lett., 1986, 27, 4141–4144.

    Article  Google Scholar 

  41. S. J. Cho, R. Ling, A. Kim, P. S. Mariano, A Versatile Approach to the Synthesis of (+)−Mannostatin A Analogues, J. Org. Chem., 2000, 65, 1574–1577.

    Article  PubMed  CAS  Google Scholar 

  42. H. Lu, P. S. Mariano, Y. Lam, A Concise Synthesis of the (−)−Allosamizoline Aminocyclopentitol Based on Pyridinium Salt Photochemistry, Tetrahedron Lett., 2001, 42, 4755–4757.

    Article  CAS  Google Scholar 

  43. W. C. Still, A. J. Mitra, A Highly Stereoselective Synthesis of Z-Trisubstituted Olefins Via [2,3]-Sigmatropic Rearrangement. Preference for a Pseudoaxially Substituted Transition State, J. Am. Chem. Soc., 1978, 100, 1927–1928.

    Article  CAS  Google Scholar 

  44. H. Lu, Z. Su, L. Song, P. S. Mariano, A Novel Approach to the Synthesis of Amino-Sugars. Routes to Selectively Protected 3-Amino-3-deoxy-aldopentoses Based on Pyridinium Salt Photochemistry, J. Org. Chem., 2002, 67, 3525–3528.

    Article  PubMed  CAS  Google Scholar 

  45. L. Song, E. N. Duesler, P. S. Mariano, Stereoselective Synthesis of Polyhydroxylated Indolizidines Based on Pyridinium Salt Photochemistry and Ring Rearrangement Metathesis, J. Org. Chem., 2004, 69, 7284–7293.

    Article  PubMed  CAS  Google Scholar 

  46. S. Randl, S. Blechert in Handbook of Metathesis, ed. R. H. Grubbs, Wiley-VCH, 2003, vol, 2, ch. 2, pp. 151–175.

  47. Z. Zhao, L. Song, P. S. Mariano, A Concise Sequential Photochemical-metathesis Approach for the Synthesis of (+)-Castanospermine and Possible Uniflorine-A Stereoisomers, Tetrahedron, 2005, 61, 8888–8894.

    Article  CAS  Google Scholar 

  48. Z. Zhao, P. S. Mariano, Application of the Photocyclization Reaction of 1,2-Cyclopentafused Pyridinium Perchlorate to Formal Total Syntheses of (−)−Cephalotaxine, Tetrahedron, 2006, 62, 7266–7273.

    Article  CAS  Google Scholar 

  49. N. Isono, M. Mori, Total Synthesis of (−)−Cephalotaxine, J. Org. Chem., 1995, 60, 115–119.

    Article  CAS  Google Scholar 

  50. L. F. Tietze, H. Schirok, Enantioselective Highly Efficient Synthesis of (−)−Cephalotaxine Using Two Palladium-Catalyzed Transformations, J. Am. Chem. Soc., 1999, 121, 10264–10269.

    Article  CAS  Google Scholar 

  51. S. Suga, M. Watanabe, J. Yoshida, Electroauxilliary-Assisted Sequential Introduction of Two Carbon Nucleophiles on the Same α-Carbon of Nitrogen: Application to the Synthesis of Spiro Compounds, J. Am. Chem. Soc., 2002, 124, 14824–14825.

    Article  PubMed  CAS  Google Scholar 

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  1. Department of Chemistry and Chemical Biology University of New Mexico, Albuquerque, New Mexico, 87131, USA

    Jiwen Zou & Patrick S. Mariano

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  1. Jiwen Zou
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  2. Patrick S. Mariano
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Correspondence to Patrick S. Mariano.

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Zou, J., Mariano, P.S. The synthetic potential of pyridinium salt photochemistry. Photochem Photobiol Sci 7, 393–404 (2008). https://doi.org/10.1039/b801808c

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