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Ti-catalyzed ring-opening oxidative amination of methylenecyclopropanes with diazenes

The ring-opening oxidative amination of methylenecyclopropanes (MCPs) with diazenes catalyzed by py 3 TiCl 2 (NR) complexes is reported. This reaction selectively generates branched α-methylene imines as opposed to linear α,β-unsaturated imines, which are difficult to access via other methods. Produ...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2020-07, Vol.11 (27), p.724-729
Main Authors: Beaumier, Evan P, Ott, Amy A, Wen, Xuelan, Davis-Gilbert, Zachary W, Wheeler, T. Alexander, Topczewski, Joseph J, Goodpaster, Jason D, Tonks, Ian A
Format: Article
Language:English
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Summary:The ring-opening oxidative amination of methylenecyclopropanes (MCPs) with diazenes catalyzed by py 3 TiCl 2 (NR) complexes is reported. This reaction selectively generates branched α-methylene imines as opposed to linear α,β-unsaturated imines, which are difficult to access via other methods. Products can be isolated as the imine or hydrolyzed to the corresponding ketone in good yields. Mechanistic investigation via density functional theory suggests that the regioselectivity of these products results from a Curtin-Hammett kinetic scenario, where reversible β-carbon elimination of a spirocyclic [2 + 2] azatitanacyclobutene intermediate is followed by selectivity-determining β-hydrogen elimination of the resulting metallacycle. Further functionalizations of these branched α-methylene imine products are explored, demonstrating their utility as building blocks. The ring-opening oxidative amination of methylenecyclopropanes (MCPs) with diazenes catalyzed by py 3 TiCl 2 (NR) complexes is reported.
ISSN:2041-6520
2041-6539
DOI:10.1039/d0sc01998d