Microwave‐assisted Transition Metal‐catalyzed Coupling Reactions

Russo, Francesco; Odell, Luke R.; Olofsson, Kristofer; Nilsson, Peter; Larhed, Mats

doi:10.1002/9783527619559.ch15

Cited by 6 publications

(1 citation statement)

References 245 publications

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“…Recently, microwaves have been shown to assist chemical transformations because of a rapid local heating. The medium must be sufficiently polar in order that the electric field and dielectric relaxation induce a rapid thermal effect, resulting in both a rapid conversion and a satisfactory selectivity . Many studies deal with microwave-promoted carbonylations, and more recently, microwave-assisted domino hydroformylation-cyclization reactions were reported for the synthesi of cyclic amines of pharmaceutical interest…”

Section: Biphasic Catalysis and Special Activation Conditionsmentioning

confidence: 99%

Tandem Hydroaminomethylation Reaction to Synthesize Amines from Alkenes

2018

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In the context of atom economy and low environmental impact, synthesis of amines by an efficient catalytic process is of great importance to produce these building blocks for fine chemical industry. The one-pot hydroaminomethylation of alkenes is a tandem reaction which involves three successive steps under CO/H pressure to perform the catalyzed hydroformylation of the alkene into the corresponding aldehyde followed by its condensation with a N-H function and the catalyzed hydrogenation of the imine/enamine intermediate into the corresponding saturated amine. Rhodium and more recently ruthenium complexes have been designed to combine high conversions of the reactants and chemoselectivity in the expected amines with high regioselectivity in either the linear or the branched amine. The coordination sphere of the metal according to the presence of ligands, temperature, CO/H partial pressures, and nature of the solvent is essential for complying with these selectivity requirements. The rate of the hydroformylation step needs to be fast with regard to the hydrogenation step. The role of amines in the coordination sphere and water, presumably in the second sphere, on the mechanism requires some more studies. Similarly, the enantioselective synthesis of amine is not yet achieved directly and interrupted processes or use of asymmetric organo-catalyzed reductive amination are efficient synthetic ways for producing chiral amines. The separation of the catalyst from the organic products by biphasic or (semi-) heterogeneized systems and its recycling have been demonstrated in many cases. The present review provides a report of the state of the art in this autotandem hydroaminomethylation catalysis and should open prospects in the design of less expensive and abundant metal complexes for reaching at low cost similar and even superior performances.

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Section: Biphasic Catalysis and Special Activation Conditionsmentioning

confidence: 99%