Bromo-nitro-sulfolene Halogen Dance

ORGN 109

Jeffrey E. Elbert, Jeffrey.Elbert@uni.edu1, Valentina M. Berestovitskaya2, Irina E. Efremova2, and Victoria V. Abzianidze2. (1) Department of Chemistry and Biochemistry, University of Northern Iowa, MSH 243, 0423, Cedar Falls, IA 50614, (2) Department of Organic Chemistry, Hertzen State Pedagogical University of Russia, St. Petersburg, Russia
Calculations using Gaussian 3 have further refined the mechanistic study of the Halogen Dance rearrangement of bromo-nitrosulfolene 1. This reaction occurs spontaneously in DMSO leading to rearrangement and disproportionation products 3-6. Previous examples reported are aromatic and heteroaromatic systems requiring strong base (BuLi, KNH2, etc.) for initiation. NMR kinetic studies and Gaussian calculations presented are used to differentiate between unimolecular and bimolecular rearrangement and between DMSO and sulfolene as the Br+ carrier. This reaction is a unique example of Halogen Dance that does not involve an aromatic system or strong base.

 

Asymmetric Reactions and Syntheses, Physical Organic Chemistry, Combinatorial Chemistry, Total Synthesis
8:00 PM-10:00 PM, Sunday, 26 March 2006 Georgia World Congress Center -- Ex. Hall B4, Poster

Division of Organic Chemistry

The 231st ACS National Meeting, Atlanta, GA, March 26-30, 2006