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Reactivity of Bispropargyl Sulfones under Basic Conditions: Interplay Between Garratt-Braverman and Schmittel/Myers-Saito Cyclization Pathway

Mukherjee, Raja and Mondal, Sayantan and Basak, Amit and Mallick, Dibyendu and Jemmis, Eluvathingal D (2012) Reactivity of Bispropargyl Sulfones under Basic Conditions: Interplay Between Garratt-Braverman and Schmittel/Myers-Saito Cyclization Pathway. In: CHEMISTRY-AN ASIAN JOURNAL, 7 (5). pp. 957-965.

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Official URL: http://dx.doi.org/10.1002/asia.201100903

Abstract

The preference for GarrattBraverman (GB) over MyersSaito (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.

Item Type: Journal Article
Keywords: antibiotics; cyclization; DNA cleavage; enediyne; sulfones
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 14 Jul 2012 03:49
Last Modified: 14 Jul 2012 03:49
URI: http://eprints.iisc.ernet.in/id/eprint/44585

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