Tuning Pd-nanoparticle@MIL-101(Cr) Catalysts for Tandem Reductive Amination

Abstract

The versatility of MOFs as highly porous Lewis acidic supports for precious metal nanoparticles has been exploited for one-pot tandem reductive amination catalysis. MIL-101(Cr) loaded with Pd nanoparticles ca. 3 nm in size at 0.2–1 wt% has been used to catalyse the reaction of 4′-fluoroacetophenone with benzylamine under 10 bar of H 2 to give the secondary amine, 4′-fluoro-α-methyl- N -phenylmethylbenzenemethanamine. For the highest Pd loading, major hydrogenolysis of the secondary amine occurs in a second tandem reaction, but by changing the ratio of Pd to Lewis acidic Cr 3+ active sites it is possible to tune the catalytic selectivity to the desired 2° amine product. An empirical kinetic analysis was performed to demonstrate this active site complementarity. Graphical Abstract Electronic supplementary material The online version of this article (doi:10.1007/s10562-017-2208-0) contains supplementary material, which is available to authorized users.

Polyimide-cellulose interaction in Sb anode enables fast charging lithium-ion battery application

“…There is no hydrogenolysis of the benzyl group or, in 1d, of the C-Br, which would be expected using typical heterogeneous hydrogenation catalysts. [16] While the SulP1-MOF-808(Hf)-Ir gave good results in reductive amination of ketones, it is well known that reduction of aldimines is significantly easier than that of ketimines and we found that SulP1-MOF-808(Hf)-Rh was able to reductively aminate benzaldehyde (Scheme 3). With this precedent, we aimed to establish the versatile nature of SulP1-MOF-808(Hf) as an insoluble "porous phosphine ligand" with Lewis acidity, whose catalytic properties can be modified by the choice of metal precursor added.…”

A Bifunctional MOF Catalyst Containing Metal–Phosphine and Lewis Acidic Active Sites

“…High conversions and selectivities were observed. There is no hydrogenolysis of the benzyl group or, in 1 d , of the C−Br moiety, which would be expected using typical heterogeneous hydrogenation catalysts …”

“…There is no hydrogenolysis of the benzylg roup or,i n1d,o ft he CÀBr moiety,w hich would be expected using typicalh eterogeneous hydrogenation catalysts. [16] Table 2. Optimisation of reductive amination.…”

One-pot amination of aldehydes and ketones over heterogeneous catalysts for production of secondary amines

“…Typically the literature on amination provides only the yields of the desired product at the end of the reaction without reporting kinetics. [1,2,23,28,29,46,47,51,52,56,[59][60][61] In some studies, the reaction conditions for transformations of aldehyde and ketones with amines or secondary amines were different. [11,15,17,23,49,54,61,62] Figure 2.…”