Mechanistic insights into hydroxy(tosyloxy)iodobenzene-mediated ditosyloxylation of chalcones: a DFT study

• Jai Parkash,
• Sangeeta Saini,
• Vaishali Saini,
• Omkar Bains and
• Raj Kamal

Beilstein J. Org. Chem. 2025, 21, 2703–2715, doi:10.3762/bjoc.21.208

• group on the migrating aryl ring favours the formation of β,β-ditosyloxy ketones while in case of electron-withdrawing groups, there are nearly equal chances of the formation of α,β-ditosyloxy ketones and β,β-ditosyloxy ketones. Keywords: 1,2-aryl-migration; chalcones; ditosyloxylation; HTIB; para

• -mediated ditosyloxylation of α,β-unsaturated carbonyl compounds (chalcones) bearing an aryl group at β-position (compound A) leading to formation of two possible products, that are: α-arylated β,β-ditosyloxy-substituted carbonyl compound (compound B – geminal product) and β-arylated α,β-ditosyloxy

• ditosyloxy ketone may not occur at all under the experimental conditions. Relative Gibbs free energy profile for HTIB-mediated ditosyloxylation of chalcone with X = -SCH3 involving 1,2-aryl migration leading to the formation of the β,β-ditosyloxy ketone. Free energies are reported in kcal/mol. Bond lengths