Chemo- and Regioselective Homogeneous Rhodium-Catalyzed Hydroamidomethylation of Terminal Alkenes to N-Alkylamides

TitleChemo- and Regioselective Homogeneous Rhodium-Catalyzed Hydroamidomethylation of Terminal Alkenes to N-Alkylamides
Publication TypeJournal Article
Year of Publication2013
AuthorsRaoufmoghaddam, S., E. Drent, E. Bouwman
JournalChemsuschem
Volume6
Issue9
Pagination1759-1773
Date PublishedSep
ISBN Number1864-5631
Accession NumberWOS:000325090400025
Keywordsaldehydes, amide formation, bite angle, chemoselectivity, complexes, highly selective hydroaminomethylation, homogeneous catalysis, hydroamidomethylation, hydroformylation, internal olefins, ketones, linear amines, reductive amination, regioselectivity, rhodium
Abstract

A rhodium/xantphos homogeneous catalyst system has been developed for direct chemo- and regioselective mono-N-alkylation of primary amides with 1-alkenes and syngas through catalytic hydroamidomethylation with 1-pentene and acetamide as model substrates. For appropriate catalyst performance, it appears to be essential that catalytic amounts of a strong acid promoter, such as p-toluenesulfonic acid (HOTs), as well as larger amounts of a weakly acidic protic promoter, particularly hexafluoroisopropyl alcohol (HORF) are applied. Apart from the product N-1-hexylacetamide, the isomeric unsaturated intermediates, hexanol and higher mass byproducts, as well as the corresponding isomeric branched products, can be formed. Under optimized conditions, almost full alkene conversion can be achieved with more than 80% selectivity to the product N-1-hexylamide. Interestingly, in the presence of a relatively high concentration of HORF, the same catalyst system shows a remarkably high selectivity for the formation of hexanol from 1-pentene with syngas, thus presenting a unique example of a selective rhodium-catalyzed hydroformylation-hydrogenation tandem reaction under mild conditions. Time-dependent product formation during hydroamidomethylation batch experiments provides evidence for aldehyde and unsaturated intermediates; this clearly indicates the three-step hydroformylation/condensation/hydrogenation reaction sequence that takes place in hydroamidomethylation. One likely role of the weakly acidic protic promoter, HORF, in combination with the strong acid HOTs, is to establish a dual-functionality rhodium catalyst system comprised of a neutral rhodium(I) hydroformylation catalyst species and a cationic rhodium(III) complex capable of selectively reducing the imide and/or ene-amide intermediates that are in a dynamic, acid-catalyzed condensation equilibrium with the aldehyde and amide in a syngas environment.

DOI10.1002/Cssc.201300484
Alternate JournalChemsuschem

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