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2-Diazo-1-(4-hydroxyphenyl)ethanone: a versatile photochemical and synthetic reagent

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Abstract

α-Diazo arylketones are well-known substrates for Wolff rearrangement to phenylacetic acids through a ketene intermediate by either thermal or photochemical activation. Likewise, α-substituted p-hydroxyphenacyl (pHP) esters are substrates for photo-Favorskii rearrangements to phenylacetic acids by a different pathway that purportedly involves a cyclopropanone intermediate. In this paper, we show that the photolysis of a series of α-diazo- p-hydroxyacetophenones and p-hydroxyphenacyl (pHP) α-esters both generate the identical rearranged phenylacetates as major products. Since α-diazo- p-hydroxyacetophenone (1a, pHP N2) contains all the necessary functionalities for either Wolff or Favorskii rearrangement, we were prompted to probe this intriguing mechanistic dichotomy under conditions favorable to the photo-Favorskii rearrangement, i.e., photolysis in hydroxylic media. An investigation of the mechanism for conversion of 1a to p-hydroxyphenyl acetic acid (4a) using time-resolved infrared (TRIR) spectroscopy clearly demonstrates the formation of a ketene intermediate that is subsequently trapped by solvent or nucleophiles. The photoreaction of 1a is quenched by oxygen and sensitized by triplet sensitizers and the quantum yields for 1a–c range from 0.19 to a robust 0.25. The lifetime of the triplet, determined by Stern–Volmer quenching, is 31 ns with a rate for appearance of 4a of k = 7.1 × 106 s−1 in aq. acetonitrile (1:1 v:v). These studies establish that the primary rearrangement pathway for 1a involves ketene formation in accordance with the photo-Wolff rearrangement. Furthermore we have also demonstrated the synthetic utility of 1a as an esterification and etherification reagent with a variety of substituted α-diazo- p-hydroxyacetophenones, using them as synthons for efficiently coupling it to acids and phenols to produce pHP protect substrates.

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Notes and references

  1. A. E. Favorskii, J. Russ. Phys.-Chem. Soc. 1894, 26, 590.

    Google Scholar 

  2. A. S. Kende, Org. React. 1960, 11, 261–316.

    CAS  Google Scholar 

  3. W. Kirmse, Eur. J. Org. Chem. 2002 2193–2256.

    Google Scholar 

  4. T. C. Celius, Y. Wang and J. P. Toscano, in CRC Handbook of Organic Photochemistry and Photobiology, ed. W. M. Horspool and F. Lenci, CRC Press, Boca Raton, FL, 2nd edn, 2004, pp.90/1–90/16.

  5. G. Burdzinski and M. S. Platz, J. Phys. Org. Chem. 2010, 23, 308–314.

    Article  CAS  Google Scholar 

  6. J. Wang, G. Burdzinski, J. Kubicki and M. S. Platz, J. Am. Chem. Soc. 2008, 130, 11195–11209.

    Article  CAS  PubMed  Google Scholar 

  7. J. C. Anderson and C. B. Reese, Tetrahedron Lett. 1962, 1, 1–4.

    Article  Google Scholar 

  8. R. S. Givens and C.-H. Park, Tetrahedron Lett. 1996, 35, 6259–6266.

    Article  Google Scholar 

  9. R. S. Givens, D. Heger, B. Hellrung, Y. Kamdzhilov, M. Mac, P. G. Conrad, E. Cope, J. I. Lee, J. F. Mata-Segreda, R. L. Schowen and J. Wirz, J. Am. Chem. Soc. 2008, 130, 3307–3309.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  10. C.-H. Park and R. S. Givens, J. Am. Chem. Soc. 1997, 119, 2453–2463.

    Article  CAS  Google Scholar 

  11. P. Klán, T. Šolomek, C. G. Bochet, A. Blanc, R. S. Givens, M. Rubina, V. Popik, A. Kostikov and J. Wirz, Chem. Rev. 2013, 113, 119–191.

    Article  PubMed  CAS  Google Scholar 

  12. M. Goeldner and R. S. Givens, Dynamic Studies in Biology, Wiley-VCH, Weinheim, Germany, 2005.

    Book  Google Scholar 

  13. G. Mayer and A. Heckel, Angew. Chem., Int. Ed. 2006, 45, 4900–4921.

    Article  CAS  Google Scholar 

  14. H.-M. Lee, D. R. Larson and D. S. Lawrence, ACS Chem. Biol. 2009, 4, 409–427.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  15. R. S. Givens, M. Rubina and J. Wirz, Photochem. Photobiol. Sci. 2012, 11, 472–488.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  16. V. B. Kammath, T. Solomek, B. P. Ngoy, D. Heger, P. Klán, M. Rubina and R. S. Givens, J. Org. Chem. 2013, 78, 1718–1729.

    Article  CAS  PubMed  Google Scholar 

  17. T. Solomek, B. P. Ngoy, D. Heger, R. Givens and P. Klan, J. Am. Chem. Soc. 2013, 135, 15209–15215.

    Article  CAS  PubMed  Google Scholar 

  18. L. Blancafort, A. Migani and Q. Li, J. Phys. Chem. Lett. 2012, 3, 1056–1061.

    Article  PubMed  CAS  Google Scholar 

  19. K. F. Stensrud, D. Heger, P. Sebej, J. Wirz and R. S. Givens, Photochem. Photobiol. Sci. 2008, 7, 614–624.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  20. K. Stensrud, J. Noh, K. Kandler, J. Wirz, D. Heger and R. S. Givens, J. Org. Chem. 2009, 74, 5219–5227.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  21. C. Ma, P. Zuo, W. M. Kwok, W. S. Chan, J. T. Z. Kan, P. H. Toy and D. L. Phillips, J. Org. Chem. 2004, 69, 6641–6657.

    Article  CAS  PubMed  Google Scholar 

  22. C. Ma, W. M. Kwok, W. S. Chan, P. Zuo, J. T. W. Kan, P. H. Toy and D. L. Phillips, J. Am. Chem. Soc. 2005, 127, 1463–1472.

    Article  CAS  PubMed  Google Scholar 

  23. W. S. Chan, W. M. Kwok and D. L. Phillips, J. Phys. Chem. A 2005, 109, 3454–3469.

    Article  CAS  PubMed  Google Scholar 

  24. C. Ma, W. M. Kwok, W. S. Chan, Y. Du, J. T. W. Kan and D. L. Phillips, J. Am. Chem. Soc. 2006, 128, 2558–2570.

    Article  CAS  PubMed  Google Scholar 

  25. P. Zuo, C. Ma, W. M. Kwok, W. Chan and D. L. Phillips, J. Org. Chem. 2005, 70, 8661–8675.

    Article  CAS  PubMed  Google Scholar 

  26. X. B. Chen, C. Ma, W. M. Kwok, X. Guan, Y. Du and D. L. Phillips, Phys. Chem. A 2006, 110, 12406–12413.

    Article  CAS  Google Scholar 

  27. G. Burdzinski, J. Kubicki, M. Sliwa, J. Réhault, Y. Zhang, B. Vyas, H. L. Luk, C. M. Hadad and M. S. Platz, J. Org. Chem. 2013, 78, 2026–2032.

    Article  CAS  PubMed  Google Scholar 

  28. L. Horner, W. Kirmse and K. Muth, Chem. Ber. 1958, 91, 430–437.

    Article  CAS  Google Scholar 

  29. J. Meinwald, A. Lewis and P. G. Gassman, J. Am. Chem. Soc. 1962, 84, 977–983.

    Article  CAS  Google Scholar 

  30. R. C. Cookson, J. Hudec, S. A. Knight and B. R. D. Whitear, Tetrahedron 1963, 19, 1995–2007.

    Article  CAS  Google Scholar 

  31. R. S. Givens, M. Rubina and K. L. Stensrud, J. Org. Chem. 2013, 78, 1709–1717.

    Article  CAS  PubMed  Google Scholar 

  32. W. Kirmse and L. Horner, Liebigs Ann. Chem. 1959, 625, 34–43.

    Article  CAS  Google Scholar 

  33. J. Wang, G. Burdzinski, J. Kubicki, T. L. Gustafson and M. S. Platz, J. Am. Chem. Soc. 2008, 130, 5418–5419.

    Article  CAS  PubMed  Google Scholar 

  34. H. Tomioka, H. Okuno and Y. Izawa, J. Org. Chem. 1980, 45, 5278–5283.

    Article  CAS  Google Scholar 

  35. T. W. Greene and P. G. M. Wutts, Greene’s Protective Groups in Organic Synthesis, John Wiley & Sons, New Jersey, United States, 4th edn, 2007.

    Google Scholar 

  36. P. G. Gassman and W. J. Greenlee, Org. Synth. 1973, 53, 38–43.

    Article  CAS  Google Scholar 

  37. J. S. Pizey, in Synthetic Reagent, Ellis Horwwd, Ltd., Chichester, England, 1977.

    Google Scholar 

  38. R. A. More O’Ferrall, Adv. Phys. Org. Chem. 1967, 5, 331–399.

    Google Scholar 

  39. A. I. Hassid, M. M. Kreevoy and T.-M. Liang, Faraday Symp. Chem. Soc. 1975, 10, 69.

    Article  CAS  Google Scholar 

  40. W. J. Albery, C. W. Conway and J. A. Hall, J. Chem. Soc., Perkin Trans. 2 1976, 4, 473–477.

    Article  Google Scholar 

  41. E. Kuehnel, D. D. P. Laffan, G. C. Lloyd-Jones, T. M. Del Campo, I. R. Shepperson and J. L. Slaughter, Angew. Chem., Int. Ed. 2007, 46, 7075–7078.

    Article  CAS  Google Scholar 

  42. M. Remeš, J. Roithová, D. Schröder, E. Cope, C. Perera, S. N. Senadheera, K. Stensrud, C.-C. Ma and R. S. Givens, J. Org. Chem. 2011, 76, 2180–2186.

    Article  PubMed  CAS  PubMed Central  Google Scholar 

  43. C.-H. Park and R. S. Givens, J. Am. Chem. Soc. 1997, 119, 2453–2463.

    Article  CAS  Google Scholar 

  44. P. G. Conrad II, R. S. Givens, J. F. W. Weber and K. Kandler, Org. Lett. 2000, 2, 1545–1547.

    Article  CAS  PubMed  Google Scholar 

  45. T. Curtius, Ber. 1883, 16, 2230–2231.

    Article  Google Scholar 

  46. (a) An earlier use of diazo pHP for the synthesis of pHP O2CCF3 (12) has been reported in ref. 17 see also (b) M. P. Doyle, M. A. McKervey and T. Ye, Modern Catalytic Methods for Organic Synthesis with Diazo Compounds, John Wiley & Sons, New York, 1998, pp. 433–486.

    Google Scholar 

  47. R. S. Givens, K. Stensrud, P. G. Conrad II, A. L. Yousef, C. Perera, S. N. Senadheera, H. Domink and J. Wirz, Can. J. Chem. 2011, 89, 364–384.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  48. T. Nagano and K. Matsumura, J. Am. Chem. Soc. 1953, 75, 6237–6238.

    Article  CAS  Google Scholar 

  49. J. Périé and T. Gefflaut, Synth. Commun. 1994, 24, 29–33.

    Article  Google Scholar 

  50. P. G. Conrad II, R. S. Givens, B. Hellrung, C. S. Rajesh and M. Ramseir, J. Am. Chem. Soc. 2000, 122, 9346–9347.

    Article  CAS  Google Scholar 

  51. P. Sebej, B. H. Lim, B. S. Park, R. S. Givens and P. Klan, Org. Lett. 2011, 13, 644–647.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  52. J. M. Goodman, J. J. Jmes and A. Whiting, J. Chem. Soc., Perkin Trans. 2 1994 109–116.

    Google Scholar 

  53. J. March, Advanced Organic Chemistry, Wiley, New York, 4th edn, 1992.

    Google Scholar 

  54. F. Kaplan and G. K. Meloy, Tetrahedron Lett. 1964 2427–2430.

    Google Scholar 

  55. F. Kaplan and G. K. Meloy, J. Am. Chem. Soc. 1966, 88, 950–956.

    Article  CAS  Google Scholar 

  56. H. Tomioka, H. Kitagawa and Y. Izawa, J. Org. Chem. 1979, 44, 3072–3075.

    Article  CAS  Google Scholar 

  57. H. Tomioka, H. Okuno and Y. Izawa, J. Org. Chem. 1980, 45, 5278–5283.

    Article  CAS  Google Scholar 

  58. G. Paliani, S. Sorriso and R. Cataliotti, J. Chem. Soc., Perkin Trans. 2 1976 707–710.

    Google Scholar 

  59. S. Sorriso, G. Piazza and A. Foffani, J. Chem. Soc. B 1971 805–809.

    Google Scholar 

  60. N. H. Werstiuk, H. M. Muchall, J. Ma and M. T. H. Liu, Can. J. Chem. 1998, 76, 1162–1173.

    Article  CAS  Google Scholar 

  61. N. H. Muchall, M. S. Pitters and M. S. Workentin, Tetrahedron 1999, 55, 3767–3778.

    Article  CAS  Google Scholar 

  62. K. Zhang, J. E. T. Corrie, V. R. N. Munasinghe and P. Wan, J. Am. Chem. Soc. 1999, 121, 5625–5632.

    Article  CAS  Google Scholar 

  63. U. Mazzucato, G. Cauzzo and A. Foffani, Tetrahedron Lett. 1963, 23, 1525–1529.

    Article  Google Scholar 

  64. J. C. Scaiano, J. Am. Chem. Soc. 1980, 102, 7747–7753.

    Article  CAS  Google Scholar 

  65. W. G. Herkstroeter, A. A. Lamola and G. S. Hammond, J. Am. Chem. Soc. 1964, 86, 4537–4540.

    Article  CAS  Google Scholar 

  66. N. J. Turro, Modern Molecular Photochemistry, Benjamin/Cummings Publishing Co. Inc., Menlo Park, 1978.

    Google Scholar 

  67. L. Pastor-Pérez, C. Wiebe, J. Pérez-Prietto and S.-E. Stiriba, J. Org. Chem. 2007, 72, 1541–1544.

    Article  PubMed  CAS  Google Scholar 

  68. P. Klan and J. Wirz, Photochemistry of Organic Compounds From Concepts to Practice, Wiley, 2009.

    Book  Google Scholar 

  69. S. L. Murov, I. Carmichael and G. L. Hug, Handbook of Photochemistry, Marcel Dekker Inc., New York, 1993.

    Google Scholar 

  70. J. G. Calvert and J. N. Pitts, Photochemistry, Wiley & Sons, New York, 1966.

    Google Scholar 

  71. G. L. Andreu, R. Delgado, J. A. Velho, C. Curti and A. E. Vercesi, Arch. Biochem. Biophys. 2005, 439, 184–193.

    Article  CAS  PubMed  Google Scholar 

  72. I. G. Gut, P. D. Wood and R. W. Redmond, J. Am. Chem. Soc. 1996, 118, 2366–2373.

    Article  CAS  Google Scholar 

  73. C. S. Rajesh, R. S. Givens and J. Wirz, J. Am. Chem. Soc. 2000, 122, 611–618.

    Article  CAS  Google Scholar 

  74. R. S. Givens and J.-I. Lee, J. Photosci. 2003, 10, 37–48.

    CAS  Google Scholar 

  75. N. R. Candeias and C. A. M. Afonso, Curr. Org. Chem. 2009, 13, 763–787.

    Article  CAS  Google Scholar 

  76. J. C. Scaiano, J. Am. Chem. Soc. 1980, 102, 7747–7753.

    Article  CAS  Google Scholar 

  77. K. Iwata and H. Hamaguchi, Appl. Spectrosc. 1990, 44, 1431–1437.

    Article  CAS  Google Scholar 

  78. T. Yuzawa, C. Kato, M. W. George and H. Hamaguchi, Appl. Spectrosc. 1994, 48, 684–690.

    Article  CAS  Google Scholar 

  79. Y. Wang, T. Yuzawa, H. Hamaguchi and J. P. Toscano, J. Am. Chem. Soc. 1999, 121, 2875–2882.

    Article  CAS  Google Scholar 

  80. B. D. Wagner, B. R. Arnold, G. S. Brown and J. Lusztyk, J. Am. Chem. Soc. 1998, 120, 1827–1834.

    Article  CAS  Google Scholar 

  81. A. D. Allen, J. D. Colomvakos, F. Diederich, I. Eagle, X. Hao, R. Liu, J. Lusztyk, J. Ma, M. A. McAllister, Y. Rubin, K. Sung, T. T. Tidwell and B. D. Wagner, J. Am. Chem. Soc. 1997, 119, 12125–12130.

    Article  CAS  Google Scholar 

  82. N. Camara de Lucas, J. C. Netto-Ferreira, J. Andraos, J. Lusztyk, B. D. Wagner and J. C. Scaiano, Tetrahedron Lett. 1997, 38, 5147–5150.

    Article  Google Scholar 

  83. B. D. Wagner, M. Z. Zgierski and J. Lusztyk, J. Am. Chem. Soc. 1994, 116, 6433–6434.

    Article  CAS  Google Scholar 

  84. J. Andraos, Y. Chiang, A. J. Kresge, I. G. Pojarlieff, N. P. Schepp and J. Wirz, J. Am. Chem. Soc. 1994, 116, 73–81.

    Article  CAS  Google Scholar 

  85. J. F. McGarrity and T. Smyth, J. Am. Chem. Soc. 1980, 102, 7303–7308.

    Article  CAS  Google Scholar 

  86. L. Wolff, Justus Liebigs Ann. Chem. 1902, 325, 129–195.

    Article  Google Scholar 

  87. C.-H. Park and R. S. Givens, J. Am. Chem. Soc. 1997, 119, 2453–2463.

    Article  CAS  Google Scholar 

  88. J. Qin, M. Xie, Z. Hu and H. Zhao, Synth. Commun. 1992, 22, 2253–2258.

    Article  CAS  Google Scholar 

  89. C. Liu, W. Gou, X. Shi, M. A. Kaium, X. Gu and Y. Z. Zhu, Eur. J. Med. Chem. 2011, 46, 3996–4009.

    Article  CAS  PubMed  Google Scholar 

  90. F. Arndt, Organic Synthesis, Collective Vol. II, Wiley & Sons, New York, 1943, pp. 165–167.

    Google Scholar 

  91. L. N. Mander and D. Beames, Aust. J. Chem. 1974, 27, 1257–1268.

    Article  Google Scholar 

  92. R. Adams and L. O. Binder, J. Am. Chem. Soc. 1941, 63, 2773–2776.

    Article  CAS  Google Scholar 

  93. B. Das, N. Ravindranath, G. Mahender and C. Ramesh, Tetrahedron 2003, 59, 1049–1054.

    Article  Google Scholar 

  94. W. W. Epstein and M. Garrossian, J. Chem. Soc., Chem. Commun. 1987 532–533.

    Google Scholar 

  95. T. Shinada, T. Kawakami, H. Sakai, I. Takada and Y. Ohfune, Tetrahedron Lett. 1998, 39, 3757–3760.

    Article  CAS  Google Scholar 

  96. R. S. Givens, A. Jung, C.-H. Park, J. Weber and W. Bartlett, J. Am. Chem. Soc. 1997, 119, 8369–8370.

    Article  CAS  Google Scholar 

  97. T. Hahn, International Tables for Crystallography, Vol. A. Space-Group Symmetry, Kluwer, Boston, 4th edn, 1996.

    Google Scholar 

  98. Data Collection: SMART Software Reference Manual, Bruker-AXS, Madison, WI, USA, 1998.

  99. Data Reduction: SAINT Software Reference Manual, Bruker-AXS, Madison, WI, USA, 1998.

  100. G. M. Sheldrick, SHELXTL Version 6.10 Reference Manual, Bruker-AXS, Madison, WI, USA, 2000.

    Google Scholar 

  101. C. G. Hatchard and C. A. Parker, Proc. R. Soc. London, Ser. A 1956, A220, 518–536.

    Google Scholar 

  102. C.-Y. Lee, E.-H. Chew and M.-L. Go, Eur. J. Med. Chem. 2010, 45, 2957–2971.

    Article  CAS  PubMed  Google Scholar 

  103. S. Wuennemann, R. Froehlich and D. Hoppe, Org. Lett. 2006, 8, 2455–2458.

    Article  CAS  Google Scholar 

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  1. Department of Chemistry, University of Kansas, Lawrence, Kansas 66045, USA

    Sanjeewa N. Senadheera & Richard S. Givens

  2. Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA

    Anthony S. Evans & John P. Toscano

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  1. Sanjeewa N. Senadheera
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  2. Anthony S. Evans
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  3. John P. Toscano
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  4. Richard S. Givens
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Correspondence to Richard S. Givens.

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This article is dedicated to the memory of Professor Nicholas J. Turro (1938–2012), one of the giants of physical-organic photochemistry upon whose shoulders many of us stood.

Electronic supplementary information (ESI) available. See DOI: 10.1039/c3pp50305d

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Senadheera, S.N., Evans, A.S., Toscano, J.P. et al. 2-Diazo-1-(4-hydroxyphenyl)ethanone: a versatile photochemical and synthetic reagent. Photochem Photobiol Sci 13, 324–341 (2014). https://doi.org/10.1039/c3pp50305d

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