Molybdenum-Catalyzed Reduction of Amides to Amines: The Mechanism Unravelled

Thursday, October 27, 2011: 7:05 PM
Room C1/C2 (San Jose Convention Center)
Renzo Arias Ugarte, Ph.D Student , Chemistry, University Of Texas At El Paso, El Paso, TX
Eduardo Cervantes, Undergraduate , Chemistry, University Of Texas At El Paso, El Paso, TX
Hemant Sharma, Ph.D , Chemistry, University Of Texas At El Paso, El Paso, TX
Keith Pannell, Ph.D , Chemistry, University Of Texas At El Paso, El Paso, TX
We recently reported the photochemical irradiation of tertiary silanes, R3SiH, to form symmetrical disiloxanes, R3SiOSiR3, using catalytic amounts of molybdenum and iron alkyl complexes (η5-C5H5)M(CO)nMe, M = Fe, n = 2 (1); M = Mo, n = 3 (2), in the presence of DMF solvent . We suggested a mechanism in which R3SiOCH2NMe2 intermediates were formed and further reacted with R3SiH to form siloxanes. We have extended this study for the synthesis of these intermediates, R3SiOCH2NMe2, using molybdenum carbonyl complexes of the type: Mo(CO)5L (L = CO, NMe3) as a catalyst in the presence of DMF.

The new siloxymethylamines are shown to further react with R3SiH, but only in the presence of the metal catalyst. This methodology represents a new synthetic approach for the synthesis of these derivatives R3SiOCH2NMe2 and sheds light on the important reduction of amides to amines..Full synthetic and characterization details of these new synthetic materials will be presented at the conference.

This research was supported by the Robert Welch Foundation (Grant AH-0546), Houston, TX.