Bulk Gold-Catalyzed Reactions of Isocyanides, Amines, and Amine N-Oxides

TitleBulk Gold-Catalyzed Reactions of Isocyanides, Amines, and Amine N-Oxides
Publication TypeJournal Article
Year of Publication2012
AuthorsKlobukowski ER, Angelici RJ, Woo LK
Journal TitleOrganometallics
Volume31
Pages2785-2792
Date Published04
Type of ArticleArticle
ISBN Number0276-7333
Accession NumberWOS:000303076600034
Keywordsaerobic oxidation, chemistry, complexes, ligands, metal-carbonyls, non-nanogold catalysis, oxygen, POLYMERIZATION, secondary-amines, surfaces
Abstract

Bulk gold powder (similar to 5-50 mu m particles) catalyzes the reactions of isocyanides with amines and amine N-oxides to produce ureas. The reaction of n-butyl isocyanide (Bu-n-N C) with di-n-propylamine and N-methylmorpholine N-oxide in acetonitrile, which was studied in the greatest detail, produced 3-butyl-1,1-dipropylurea (O=C((NHBu)-Bu-n)((NPr2)-Pr-n)) in 99% yield at 60 degrees C within 2 h. Sterically and electronically different isocyanides, amines, and amine N-oxides react successfully under these conditions. Detailed studies support a two-step mechanism that involves a gold-catalyzed reaction of adsorbed isocyanide with the amine N-oxide to form an isocyanate (RN=C=O), which rapidly reacts with the amine to give the urea product. These investigations show that bulk gold, despite its reputation for poor catalytic activity, is capable of catalyzing these reactions.

URL<Go to ISI>://WOS:000303076600034
DOI10.1021/om201068g
Alternate JournalOrganometallics