The Profound Effect of the Ring Size in the Electrocyclic Opening of Cyclobutene-Fused Bicyclic Systems†
Michael J. Ralph
School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS (UK) http://www.chm.bris.ac.uk/org/bmilburn/index2.htm
Search for more papers by this authorProf. Dr. David C. Harrowven
Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ (UK)
Search for more papers by this authorDr. Steven Gaulier
Syngenta UK, Jealott's Hill International Research Centre, Bracknell, Berkshire, RG42 6EY (UK)
Search for more papers by this authorDr. Sean Ng
Syngenta UK, Jealott's Hill International Research Centre, Bracknell, Berkshire, RG42 6EY (UK)
Search for more papers by this authorCorresponding Author
Prof. Dr. Kevin I. Booker-Milburn
School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS (UK) http://www.chm.bris.ac.uk/org/bmilburn/index2.htm
School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS (UK) http://www.chm.bris.ac.uk/org/bmilburn/index2.htmSearch for more papers by this authorMichael J. Ralph
School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS (UK) http://www.chm.bris.ac.uk/org/bmilburn/index2.htm
Search for more papers by this authorProf. Dr. David C. Harrowven
Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ (UK)
Search for more papers by this authorDr. Steven Gaulier
Syngenta UK, Jealott's Hill International Research Centre, Bracknell, Berkshire, RG42 6EY (UK)
Search for more papers by this authorDr. Sean Ng
Syngenta UK, Jealott's Hill International Research Centre, Bracknell, Berkshire, RG42 6EY (UK)
Search for more papers by this authorCorresponding Author
Prof. Dr. Kevin I. Booker-Milburn
School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS (UK) http://www.chm.bris.ac.uk/org/bmilburn/index2.htm
School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS (UK) http://www.chm.bris.ac.uk/org/bmilburn/index2.htmSearch for more papers by this authorWe thank the EPSRC Bristol Chemical Synthesis Doctoral Training Centre (EP/G036764/1) and Syngenta for Ph.D. studentship funding (M.J.R.).
Abstract
Fused cyclobutenes, prepared by the photocycloaddition of propargyl alcohols to cyclic anhydride chromophores, undergo facile thermochemical ring opening to fused γ-lactones. The size of the fused ring profoundly influences the temperature that is required to facilitate the ring opening (from 50 °C to 180 °C) and the nature of the product that is formed. Our studies provide new insights into the mechanistic course of these reactions and have been extended to facilitate the preparation of lactams fused to medium-sized rings.
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References
- 1T. V. Nguyen, J. M. Hartmann, D. Enders, Synthesis 2013, 45, 845.
- 2N. A. Petasis, M. A. Patane, Tetrahedron 1992, 48, 5757.
- 3J. D. White, M. P. Dillon, R. J. Butlin, J. Am. Chem. Soc. 1992, 114, 9673.
- 4
- 4aK. C. Nicolaou, F. van Delft, T. Ohshima, D. Vourloumis, J. Xu, S. Hosokawa, J. Pfefferkorn, S. Kim, T. Li, Angew. Chem. Int. Ed. Engl. 1997, 36, 2520; Angew. Chem. 1997, 109, 2630;
- 4bX.-T. Chen, S. K. Bhattacharya, B. Zhou, C. E. Gutteridge, T. R. R. Pettus, S. J. Danishefsky, J. Am. Chem. Soc. 1999, 121, 6563.
- 5K. B. Wiberg, Angew. Chem. Int. Ed. Engl. 1986, 25, 312; Angew. Chem. 1986, 98, 312.
- 6T. Bach, J. P. Hehn, Angew. Chem. Int. Ed. 2011, 50, 1000; Angew. Chem. 2011, 123, 1032.
- 7
- 7aK. I. Booker-Milburn, J. K. Cowell, F. D. Jiménez, A. Sharpe, A. J. White, Tetrahedron 1999, 55, 5875;
- 7bC. Roscini, K. L. Cubbage, M. Berry, A. J. Orr-Ewing, K. I. Booker-Milburn, Angew. Chem. Int. Ed. 2009, 48, 8716; Angew. Chem. 2009, 121, 8872;
- 7cK. L. Cubbage, A. J. Orr-Ewing, K. I. Booker-Milburn, Angew. Chem. Int. Ed. 2009, 48, 2514; Angew. Chem. 2009, 121, 2552.
- 8
- 8aD. C. Harrowven, M. Mubina, T. P. Gonçalves, R. J. Whitby, D. Bolien, H. F. Sneddon, Angew. Chem. Int. Ed. 2012, 51, 4405; Angew. Chem. 2012, 124, 4481;
- 8bD. C. Harrowven, D. D. Pascoe, I. L. Guy, Angew. Chem. Int. Ed. 2007, 46, 425; Angew. Chem. 2007, 119, 429.
- 9
- 9aK. I. Booker-Milburn, J. K. Cowell, L. J. Harris, Tetrahedron 1997, 53, 12319.
- 10
- 10aK. I. Booker-Milburn, F. D. Jiménez, A. Sharpe, Synlett 1995, 735;
- 10bK. I. Booker-Milburn, F. Delgado Jiménez, A. Sharpe, Tetrahedron 1999, 55, 5889.
- 11R. B. Woodward, R. Hoffmann, Angew. Chem. Int. Ed. Engl. 1969, 8, 781; Angew. Chem. 1969, 81, 797.
- 12
- 12aG. Binsch, J. D. Roberts, J. Am. Chem. Soc. 1965, 87, 5157;
- 12bA. C. Cope, W. R. Moore, R. D. Bach, H. J. S. Winkler, J. Am. Chem. Soc. 1970, 92, 1243;
- 12cW. G. Dauben, D. M. Michno, J. Am. Chem. Soc. 1981, 103, 2284;
- 12dW. G. Dauben, J. E. Haubrich, J. Org. Chem. 1988, 53, 600;
- 12eJ.-P. Deprés, B. Navarro, A. E. Greene, Tetrahedron 1989, 45, 2989;
- 12fW. J. Leigh, K. Zheng, K. B. Clark, J. Org. Chem. 1991, 56, 1574;
- 12gH. S. Yeom, J. Koo, H.-S. Park, Y. Wang, Y. Liang, Z.-X. Yu, S. Shin, J. Am. Chem. Soc. 2012, 134, 208.
- 13
- 13aJ. S. McConaghy, Jr., J. J. Bloomfield, Tetrahedron Lett. 1969, 10, 3719;
10.1016/S0040-4039(01)88496-3 Google Scholar
- 13bJ. S. McConaghy, Jr., J. J. Bloomfield, A. G. Hortmann, Tetrahedron Lett. 1969, 10, 3723.
10.1016/S0040-4039(01)88497-5 Google Scholar
- 14
- 14aJ. E. Baldwin, S. S. Gallagher, P. A. Leber, A. S. Raghavan, R. Shukla, J. Org. Chem. 2004, 69, 7212;
- 14bJ. E. Baldwin, S. S. Gallagher, P. A. Leber, A. S. Raghavan, Org. Lett. 2004, 6, 1457.
- 15
- 15aC. S. Loṕez, O. N. Faza, Á. R. de Lera, Chem. Eur. J. 2007, 13, 5009;
- 15bC. S. Loṕez, O. N. Faza, Á. R. de Lera, Org. Lett. 2006, 8, 2055.
- 16X.-N. Wang, E. H. Krenske, R. C. Johnston, K. N. Houk, R. P. Hsung, J. Am. Chem. Soc. 2014, 136, 9802.
- 17
- 17aJ. M. Um, H. Xu, K. N. Houk, W. Tang, J. Am. Chem. Soc. 2009, 131, 6664;
- 17bP. S. Lee, X. Zhang, K. N. Houk, J. Am. Chem. Soc. 2003, 125, 5072;
- 17cW. R. Dolbier, Jr., H. Koroniak, K. N. Houk, C. Sheu, Acc. Chem. Res. 1996, 29, 471.
- 18T. Yoshimitsu, Y. Arano, T. Kaji, T. Ino, H. Nagaoka, T. Tanaka, Heterocycles 2009, 77, 179.
- 19B. D. A. Hook, W. Dohle, P. R. Hirst, M. Pickworth, M. B. Berry, K. I. Booker-Milburn, J. Org. Chem. 2005, 70, 7558.
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