Green and efficient synthesis of sulfonamides catalyzed by nano-Ru/Fe(3)O(4).
The environmentally benign synthesis of carbon-nitrogen bonds continues to be an active and challenging field of chemical research. Here, a novel, environmentally benign method for the direct coupling of sulfonamides and alcohols is described. Despite the importance of sulfonamide derivatives as intermediates in drug synthesis, till now such transformations are rarely known. For the first time a domino dehydrogenation-condensation-hydrogenation sequence of alcohols and sulfonamides has been realized in the presence of a nanostructured catalyst. The magnetic property of the catalyst system allows for convenient isolation of the product and efficient recycling of the catalyst. A variety of coupling reactions of benzylic alcohols and sulfonamides including various heterocycles were successfully realized, often with >80% isolated yield. Advantageously, only one equivalent of the primary alcohol is consumed in the process. Mechanistic investigations of the competitive reactions of benzyl alcohol and d(7)-benzyl alcohol with p-toluenesulfonamide revealed a kinetic isotope effect (k(H)/k(D)) of 2.86 (+/-0.109) for the dehydrogenation of benzyl alcohol and 0.74 (+/-0.021) for the hydrogenation of N-benzylidene-p-toluenesulfonamide intermediate, which suggests dehydrogenation of the alcohol to be the rate determining step.
Shi
Feng
F
Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany.
Tse
Man Kin
MK
Zhou
Shaolin
S
Pohl
Marga-Martina
MM
Radnik
Jörg
J
Hübner
Sandra
S
Jähnisch
Klaus
K
Brückner
Angelika
A
Beller
Matthias
M
D000438:Alcohols / Q000737:chemistry; D002384:Catalysis; D052203:Ferrosoferric Oxide / Q000737:chemistry*; D053768:Metal Nanoparticles / Q000737:chemistry*; D046529:Microscopy, Electron, Transmission; D012428:Ruthenium / Q000737:chemistry*; D013449:Sulfonamides / Q000737:chemistry*; D014961:X-Ray Diffraction
D000438:Alcohols; D013449:Sulfonamides; D012428:Ruthenium; D052203:Ferrosoferric Oxide