Rate Coefficients for Intramolecular Homolytic Substitution of Oxyacyl Radicals at Sulfur

Article

<< Previous

Next >>

Contents Vol 66(3)

doi:10.1071/CH12477

An international journal for chemical science

	Search




	Advanced Search



	Journal Home

	About the Journal

	Editorial Board

	Contacts

	For Advertisers



	Content

	Online Early

	Current Issue

	Just Accepted

	All Issues

	Virtual Issues

	Special Issues

	Research Fronts

	Sample Issue

	Covers



	For Authors

	General Information

	Notice to Authors

	Submit Article

	Open Access



	For Referees

	Referee Guidelines

	Review Article



	For Subscribers

	Subscription Prices

	Customer Service

	Print Publication Dates

e-Alerts

Subscribe to our Email Alert or

feeds for the latest journal papers.

Connect with us

Affiliated with RACI

Royal Australian
Chemical Institute

Rate Coefficients for Intramolecular Homolytic Substitution of Oxyacyl Radicals at Sulfur

Heather M. Aitken ^A ^B, Sonia M. Horvat ^A ^B, Michelle L. Coote ^A ^C, Ching Yeh Lin ^A ^C and Carl H. Schiesser ^A ^B ^D

^A ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, Australia.
^B School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne, Melbourne, Vic. 3010, Australia.
^C Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia.
^D Corresponding author. Email: carlhs@unimelb.edu.au

Australian Journal of Chemistry 66(3) 323-329 http://dx.doi.org/10.1071/CH12477
Submitted: 19 October 2012 Accepted: 29 November 2012 Published: 18 January 2013





	PDF (767 KB) $25



	Supplementary Material



	Export Citation

Print







Comments

Abstract

It is predicted on the basis of ab initio and density functional calculations that intramolecular homolytic substitution of oxyacyl radicals at the sulfur atom in ω-alkylthio-substituted radicals do not involve hypervalent intermediates. With tert-butyl as the leaving radical, free energy barriers ΔG^‡ (G3(MP2)-RAD) for these reactions range from 45.8 kJ mol^–1 for the formation of the five-membered cyclic thiocarbonate (8) to 56.7 kJ mol^–1 for the formation of the six-membered thiocarbonate (9). Rate coefficients in the order of 10⁴–10⁶ s^–1 and 10¹–10⁴ s^–1 for the formation of 8 and 9, respectively, at 353.15 K in the gas phase are predicted at the G3(MP2)-RAD level of theory.

References

[1] A. L. J. Beckwith, C. H. Schiesser, Org. Biomol. Chem. 2011, 9, 1736. and references cited therein.
| CrossRef | CAS |

[2] Encyclopedia of Radicals in Chemistry, Biology and Materials (Eds C. Chatgilialoglu, A. Studer) 2012 (John Wiley and Sons: Chichester).

[3] A. L. J. Beckwith, Tetrahedron 1981, 37, 3073.
| CrossRef | CAS |

[4] A complete list of references is impossible to provide. See: B. Giese, Radicals in Organic Synthesis: Formation of Carbon–Carbon Bonds 1986 (Pergamon Press: Oxford), and references cited therein.

[5] A. L. J. Beckwith, C. H. Schiesser, Tetrahedron 1985, 41, 3925.
| CrossRef | CAS |

[6] D. C. Spellmeyer, K. N. Houk, J. Org. Chem. 1987, 52, 959.
| CrossRef | CAS |

[7] C. H. Schiesser, Chem. Commun. 2006, 4055.
| CAS |

[8] C. H. Schiesser, L. M. Wild, Tetrahedron 1996, 52, 13265.
| CrossRef | CAS |

[9] J. C. Walton, Acc. Chem. Res. 1998, 31, 99.
| CrossRef | CAS |

[10] S. H. Kyne, C. H. Schiesser, in Encyclopedia of Radicals in Chemistry, Biology and Materials Vol. 2 (Eds C. Chatgilialoglu, A. Studer) 2012, pp. 629–654 (John Wiley and Sons: Chichester).

[11] J. Malmström, M. Jonsson, A. Cotgreave, L. Hammarström, M. Sjodin, L. Engman, J. Am. Chem. Soc. 2001, 123, 3434.
| CrossRef |

[12] A. L. J. Beckwith, D. R. Boate, J. Chem. Soc. Chem. Commun. 1986, 189.
| CrossRef | CAS |

[13] J. Coulomb, V. Certal, M.-H. Larraufie, C. Ollivier, J.-P. Corbet, G. Mignani, L. Fensterbank, E. Lacôte, M. Malacria, Chem. – Eur. J. 2009, 15, 10225.
| CrossRef | CAS |

[14] C. H. Schiesser, H. Matsubara, I. Ritsner, U. Wille, Chem. Commun. 2006, 1067.
| CrossRef | CAS |

[15] C. H. Schiesser, U. Wille, H. Matsubara, I. Ryu, Acc. Chem. Res. 2007, 40, 303.
| CrossRef | CAS |

[16] S. H. Kyne, C. H. Schiesser, H. Matsubara, J. Org. Chem. 2008, 73, 427.
| CrossRef | CAS |

[17] S. M. Horvat, C. H. Schiesser, New J. Chem. 2010, 34, 1692.
| CrossRef | CAS |

[18] I. Ryu, K. Matsu, S. Minakata, M. Komatsu, J. Am. Chem. Soc. 1998, 120, 5838.
| CrossRef | CAS |

[19] I. Ryu, K. Okuda, K. Nagahara, N. Kambe, M. Komatsu, N. Sonoda, J. Org. Chem. 1997, 62, 7550.
| CrossRef | CAS |

[20] S. M. Horvat, C. H. Schiesser, Tetrahedron 2012, 68, 10482.
| CrossRef | CAS |

[21] S. H. Kyne, C. H. Schiesser, H. Matsubara, Org. Biomol. Chem. 2007, 5, 3938.
| CrossRef | CAS |

[22] M. A. Lucas, C. H. Schiesser, J. Org. Chem. 1998, 63, 3032.
| CrossRef | CAS |

[23] P. A. Simakov, F. N. Martinez, J. H. Horner, M. Newcomb, J. Org. Chem. 1998, 63, 1226.
| CrossRef | CAS |

[24] S. Lobachevsky, C. H. Schiesser, C. Lin, M. L. Coote, J. Phys. Chem. A 2008, 112, 13622.
| CrossRef | CAS |

[25] S. H. Kyne, C. Y. Lin, I. Ryu, M. L. Coote, C. H. Schiesser, Chem. Commun. 2010, 46, 6521.
| CrossRef | CAS |

[26] H. M. Aitken, A. N. Hancock, C. H. Schiesser, Chem. Commun. 2012, 48, 8326.
| CrossRef | CAS |

[27] H. M. Aitken, S. M. Horvat, C. H. Schiesser, C. Y. Lin, M. L. Coote, Int. J. Chem. Kinet. 2012, 44, 51.
| CrossRef | CAS |

[28] P. E. Macdougall, H. M. Aitken, Y. Kavanagh, P. J. Scammells, S. H. Kyne, C. H. Schiesser, Chem. Commun. 2012, 48, 9126.
| CrossRef | CAS |

[29] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Gaussian 09, Revision A.1 2009 (Gaussian, Inc.: Wallingford, CT).

[30] H. J. Werner, P. J. Knowles, R. Lindh, F. R. Manby, M. Schutz, P. Celani, T. Korona, G. Rauhut, R. D. Amos, A. Bernhardsson, A. Berning, D. L. Cooper, M. J. O. Deegan, A. J. Dobbyn, F. Eckert, C. Hampel, G. Hetzer, A. W. Lloyd, S. J. McNicholas, W. Meyer, M. E. Mura, A. Nicklass, P. Palmieri, R. Pitzer, U. Schumann, H. Stoll, A. J. Stone, R. Tarroni, T. Thorsteinsson, MOLPRO, Version 2009.1: A Package of Ab Initio Programs 2009 (University College Cardiff Consultants Limited: Cardiff).

[31] A. P. Scott, L. Radom, J. Phys. Chem. 1996, 100, 16502.
| CrossRef | CAS |

[32] D. J. Henry, M. B. Sullivan, L. Radom, J. Chem. Phys. 2003, 118, 4849.
| CrossRef | CAS |

[33] D. G. Truhlar, B. C. Garrett, S. J. Klippenstein, J. Phys. Chem. 1996, 100, 12771.
| CrossRef | CAS |

[34] C. Y. Lin, E. I. Izgorodina, M. L. Coote, J. Phys. Chem. A 2008, 112, 1956.
| CrossRef | CAS |

[35] C. H. Schiesser, L. M. Wild, J. Org. Chem. 1999, 64, 1131.
| CrossRef | CAS |

[36] A. C. Neves, H. M. Aitken, S. H. Kyne, L. Fensterbank, E. Lacôte, M. Malacria, C. Ollivier, C. H. Schiesser, Tetrahedron 2012, 68, 323.
| CrossRef | CAS |

[37] M. L. Coote, C. Y. Lin, A. L. J. Beckwith, A. A. Zavitsas, Phys. Chem. Chem. Phys. 2010, 12, 9597.
| CrossRef | CAS |

[38] A. L. J. Beckwith, S. A. M. Duggan, J. Chem. Soc., Perkin Trans. 2 1994, 1509.
| CrossRef | CAS |

[39] J. A. Franz, D. H. Roberts, K. F. Ferris, J. Org. Chem. 1987, 52, 2256.
| CrossRef | CAS |

[40] D. Griller, K. U. Ingold, P. J. Krusic, H. Fischer, J. Am. Chem. Soc. 1978, 100, 6750.
| CrossRef | CAS |

[41] T. Morihovitis, C. H. Schiesser, M. A. Skidmore, J. Chem. Soc., Perkin Trans. 2 1999, 2041.
| CrossRef | CAS |

Subscriber Login

	Username: Password:

Comment on this article

Legal & Privacy | Contact Us | Help