Journal
ADVANCED SYNTHESIS & CATALYSIS
Volume 351, Issue 17, Pages 2949-2958Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/adsc.200900490
Keywords
alcohols; alkylation; C-N bond formation; copper catalysts; sulfonamides
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Funding
- Chinese Academy of Sciences
- DFG [SPP 1118]
- Alexander-von-Humboldt-Stiftung
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The N-alkylation of sulfonamides with alcohols is efficiently performed in the presence of easily available copper catalysts via hydrogen borrowing methodology. Applying a copper acetate/potassium carbonate system the reaction of sulfonamides and alcohols gave the corresponding secondary amines in excellent yield. In situ HR-MS analysis indicated that bissulfonylated amines are formed under air atmosphere, which act as self-stabilizing ligands for the catalytic system. UV-visible measurements suggest the interaction between the copper centre and the bissulfonylated amine. Reactions of benzyl alcohol-d(7) with p-toluenesulfonalnide, N-benzyl-p-toluenesulfonamide or N-benzylidenetoluenesulfonamide revealed that the reaction proceeds via a transfer hydrogenation mechanism and the whole process is micro-reversible. Competitive reactions of benzyl alcohol and benzyl alcohol-d(7) with p-toluenesulfonamide revealed a kinetic isotope effect (kH/kD) of 3.287 (0.1.92) for the dehydrogenation of benzyl alcohol and 0.611 (0.033) for the hydrogenation of the N-benzylidene-p-toluenesulfonamide intermediate, which suggests that dehydrogenation of the alcohol is the rate-determining step.
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