Display options
Cite
Crespi S, Protti S, Ravelli D, et al. Sugar-Assisted Photogeneration of Didehydrotoluenes from Chlorobenzylphosphonic Acids. J Org Chem. 2017;82(23):12162-12172doi: 10.1021/acs.joc.7b01963.
Crespi, S., Protti, S., Ravelli, D., Merli, D., & Fagnoni, M. (2017). Sugar-Assisted Photogeneration of Didehydrotoluenes from Chlorobenzylphosphonic Acids. The Journal of organic chemistry, 82(23), 12162-12172. https://doi.org/10.1021/acs.joc.7b01963
Crespi, Stefano, et al. "Sugar-Assisted Photogeneration of Didehydrotoluenes from Chlorobenzylphosphonic Acids." The Journal of organic chemistry vol. 82,23 (2017): 12162-12172. doi: https://doi.org/10.1021/acs.joc.7b01963
Crespi S, Protti S, Ravelli D, Merli D, Fagnoni M. Sugar-Assisted Photogeneration of Didehydrotoluenes from Chlorobenzylphosphonic Acids. J Org Chem. 2017 Dec 01;82(23):12162-12172. doi: 10.1021/acs.joc.7b01963. Epub 2017 Nov 20. PMID: 29019237.
Copy Download .nbib Format: NLM
Share it on

J Org Chem. 2017 Dec 01;82(23):12162-12172. doi: 10.1021/acs.joc.7b01963. Epub 2017 Nov 20.

Sugar-Assisted Photogeneration of Didehydrotoluenes from Chlorobenzylphosphonic Acids.

The Journal of organic chemistry

Stefano Crespi, Stefano Protti, Davide Ravelli, Daniele Merli, Maurizio Fagnoni

Affiliations

  1. PhotoGreen Lab, Department of Chemistry, University of Pavia , Viale Taramelli 12, 27100 Pavia, Italy.

PMID: 29019237 DOI: 10.1021/acs.joc.7b01963

Abstract

Irradiation of the three isomeric chlorobenzylphophonic acids in aqueous buffer led to a pH-dependent photochemistry. Under acidic conditions (pH = 2.5), photocleavage of the Ar-Cl bond occurred and a phenyl cation chemistry resulted. Under basic conditions (pH = 11), a photoinduced release of the chloride anion followed by the detachment of the metaphosphate anion gave α,n-didehydrotoluene diradicals (α,n-DHTs), potential DNA cleaving intermediates. At a physiological pH (pH = 7.2), both a cationic and a diradical reactivity took place depending on the phosphonic acid used. It is noteworthy that the complexation exerted by a monosaccharide (glucose or methylglucopyranoside) present in solution induced an exclusive formation of α,n-DHTs. The mechanistic scenario of the different photoreactivities occurring when changing the pH of the solution and the role of the various intermediates (phenyl cations, diradicals, etc.) in the process was studied by computational analysis.

Publication Types