Reactions of triflate esters and triflamides with an organic neutral super-electron-donorThis article is part of the Organic & Biomolecular Chemistry 10th Anniversary issue.Electronic supplementary information (ESI) available. See DOI: 10.1039/c2ob25116g

• Main Authors: Jolly, Phillip I, Fleary-Roberts, Nadia, O'Sullivan, Steven, Doni, Eswararao, Zhou, Shengze, Murphy, John A
• Format: Article
• Language: English
• ISSN: 1477-0520; 1477-0539
• DOI: 10.1039/c2ob25116g

The bis-pyridinylidene 13 converts aliphatic and aryl triflate esters to the corresponding alcohols and phenols respectively, using DMF as solvent, generally in excellent yields. While the deprotection of aryl triflates has been seen with other reagents and by more than one mechanism, the deprotection of alkyl triflates is a new reaction. Studies with 18 O labelled DMF indicate that the C-O bond stays intact and hence it is the S-O bond that cleaves, underlining that the cleavage results from the extraordinary electron donor capability of 13 . Trifluoromethanesulfonamides are converted to the parent amines in like manner, representing the first cleavage of such substrates by a ground-state organic reducing reagent. The bis-pyridinylidene 13 converts aliphatic and aryl triflate esters to the corresponding alcohols and phenols respectively, using DMF as solvent, generally in excellent yields.