Modeling heterogeneous catalysts with homogeneous catalysts. Comparison of catalytic exchange of deuterium for hydrogen at the .alpha. and .beta. positions of tertiary amines by using either palladium black or dodecacarbonyltriruthenium

Transition-Metal-Catalyzed Cleavage of C–N Single Bonds

“… , The C–N bonds of tertiary amines were activated in these situations. These transformation conditions were milder than those reported for heterogeneous Pd/C catalysts . It should be mentioned that this alkyl exchange reaction is reversible.…”

Hydrogen Autotransfer in the N-Alkylation of Amines and Related Compounds using Alcohols and Amines as Electrophiles

“…206 This catalyst was also able to catalyze the hydrogen-deuterium exchange in tertiary amines from deuterium oxide, showing a very high selectivity toward R versus β position. 207 Perhaps, the bisruthenium complex depicted in Table 41 is the most useful catalyst for the reaction described along this section. Different aromatic amines 53 (200 mol %) could be alkylated with primary amines 80 to afford the corresponding secondary amines 130 with excellent yields.…”

Stereoretentive C−H Bond Activation in the Aqueous Phase Catalytic Hydrogenation of Amino Acids to Amino Alcohols

“…Related catalytic H/D exchange processes have long been known, but they were typically run in organic solvents and we have found little discussion of their stereochemistry. 12 Such reactions are thought to form imine intermediates, enabling alkyl group transfers via transamination pathways. 13 Indeed, alkyl group exchange via catalytic activation of amines has been explored as a process to convert primary to secondary and tertiary amines.…”

“…The discovery of stereoretentive C−H bond activation at amine-bearing sp 3 C sites was the most unexpected finding in this work. Related catalytic H/D exchange processes have long been known, but they were typically run in organic solvents and we have found little discussion of their stereochemistry . Such reactions are thought to form imine intermediates, enabling alkyl group transfers via transamination pathways .…”