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

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 intermolecu...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2009-12, Vol.131 (51), p.18246-18247
Main Authors: Leitch, David C, Payne, Philippa R, Dunbar, Christine R, Schafer, Laurel L
Format: Article
Language:English
Subjects:
Alkenes - chemistry
Alkynes - chemistry
Amination
Amines - chemistry
Catalysis
Cyclization
Ligands
Urea
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Summary: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 α-alkylation when forming 6- and 7-membered rings from aminoalkenes.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja906955b