Ligand effects, solvent cooperation, and large kinetic solvent deuterium isotope effects in gold(I)-catalyzed intramolecular alkene hydroamination

Kinetic studies on the intramolecular hydroamination of protected variants of 2,2-diphenylpent-4-en-1-amine were carried out under a variety of conditions with cationic gold catalysts supported by phosphine ligands. The impact of ligand on gold, protecting group on nitrogen, and solvent and additive...

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Bibliographic Details
Published in:Beilstein journal of organic chemistry 2024-02, Vol.20 (1), p.479-496
Main Authors: Lan, Ruichen, Yager, Brock, Jee, Yoonsun, Day, Cynthia S, Jones, Amanda C
Format: Article
Language:English
Subjects:
alkene hydroamination
Chemistry
Full Research Paper
general acid catalysis
gold catalysis
isotope effect
phosphine ligand effect
solvent effect
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Summary:Kinetic studies on the intramolecular hydroamination of protected variants of 2,2-diphenylpent-4-en-1-amine were carried out under a variety of conditions with cationic gold catalysts supported by phosphine ligands. The impact of ligand on gold, protecting group on nitrogen, and solvent and additive on reaction rates was determined. The most effective reactions utilized more Lewis basic ureas, and more electron-withdrawing phosphines. A DCM/alcohol cooperative effect was quantified, and a continuum of isotope effects was measured with low KIE's in the absence of deuterated alcoholic solvent, increasing to large solvent KIE's when comparing reactions in pure MeOH to those in pure MeOH- . The effects are interpreted both within the context of a classic gold π-activation/protodeauration mechanism and a general acid-catalyzed mechanism without intermediate gold alkyls.
ISSN:1860-5397
1860-5397
DOI:10.3762/bjoc.20.43