title: Reactivity of bispropargyl sulfones under basic conditions: interplay between Garratt-Braverman and Schmittel/Myers-Saito cyclization pathway.
abstract: The preference for Garratt-Braverman (GB) over Myers-Saito (MS) and Schmittel (SCM) cyclizations has recently been demonstrated in sulfones capable of undergoing all three of the processes. As the GB cyclization is a self-quenching process, there is a need to change the selectivity to the non-self-quenching MS or SCM pathway so as to enhance the DNA-cleaving efficiency that operates through the radical-mediated process. Herein we report a conformational constraint-based strategy developed by using computations (M06-2X/6-31+G*) to switch the selectivity from GB to MS/SCM pathway which also results in greater DNA-cleavage activity. The preference for GB could be brought back by easing the constraint with the help of spacers.
authors.affiliation: Department of Chemistry, Indian Institute of Technology, Kharagpur 721 302, India.
authors.forename: Raja
authors.initials: R
authors.lastname: Mukherjee
authors.forename: Sayantan
authors.initials: S
authors.lastname: Mondal
authors.forename: Amit
authors.initials: A
authors.lastname: Basak
authors.forename: Dibyendu
authors.initials: D
authors.lastname: Mallick
authors.forename: Eluvathingal D
authors.initials: ED
authors.lastname: Jemmis
mesh_terms: D000900:Anti-Bacterial Agents / Q000737:chemistry* / Q000494:pharmacology*; D003198:Computer Simulation; D018360:Crystallography, X-Ray; D003500:Cyclization; D004247:DNA / Q000378:metabolism; D053837:DNA Cleavage / Q000187:drug effects*; D008958:Models, Molecular; D008968:Molecular Conformation; D013450:Sulfones / Q000737:chemistry* / Q000494:pharmacology*
chemical_list: D000900:Anti-Bacterial Agents; D013450:Sulfones; D004247:DNA