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Broadening the Scope of Group 4 Hydroamination Catalysis Using a Tethered Ureate Ligand

TitleBroadening the Scope of Group 4 Hydroamination Catalysis Using a Tethered Ureate Ligand
Publication TypeJournal Article
Year of Publication2009
AuthorsLeitch, DC, Payne, PR, Dunbar, CR, Schafer, LL
JournalJournal of the American Chemical Society
Volume131
Pagination18246-+
Date PublishedDec
Type of ArticleArticle
ISBN Number0002-7863
KeywordsALKYNES, AMIDATE COMPLEXES, AMINES, AMINOALKENES, BOND FORMATION, INTRAMOLECULAR HYDROAMINATION, METAL-CATALYSTS, TITANIUM, UNACTIVATED ALKENES, ZIRCONIUM
Abstract

A broadly applicable group-4-based precatalyst for the hydroamination of primary and secondary amines was developed. Screening experiments involving a series of amide and urea proligands led to the discovery of a tethered bis(ureate) zirconium complex with unprecedented reactivity in the intermolecular hydroamination of alkynes and the intramolecular hydroamination of alkenes. This catalyst system is effective with primary and secondary amines, 1,2-disubstituted alkenes, and heteroatom-containing functional groups, including ethers, silanes, amines, and heteroaromatics. The gem-disubstituent effect is not required for cyclization. The catalyst is generally regioselective for the anti-Markovnikov product of intermolecular alkyne hydroamination, and chemoselective for hydroamination over alpha-alkylation when forming 6- and 7-membered rings from aminoalkenes.

URL<Go to ISI>://000273615800028