An unexpected two-group migration involving a sulfonynamide to nitrile rearrangement.: Mechanistic studies of a thermal N → C tosyl rearrangement

We report the discovery of the first double-barreled thermal rearrangement of a sulfonynamide and a methoxybenzyl to a nitrile and the first rearrangement of an SO2 group from sulfonamide to ketoimine. The rearrangement occurs under surprisingly mild conditions (onset at 100 degreesC in the melt).