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![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)
Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
Published on: March 20, 2014
Cu(I) complexes with a noninnocent PNP ligand: selective dearomatization and electrophilic addition reactivity
Jarl Ivar van der Vlugt1, Evgeny A Pidko, Dieter Vogt
1Supramolecular & Homogeneous Catalysis Group, van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, The Netherlands. j.i.vandervlugt@uva.nl
Abstract:
The neutral, T-shaped complex Cu(I)(PN(-)P(tBu)) (2), featuring a dearomatized 2,6-bis(diphosphino)pyridine (PNP)-pincer ligand, is shown to interact rapidly with electrophiles. This has enabled the synthesis of acetato complex 3. Furthermore, C-C bond formation onto the deprotonated methylene-bridgehead carbon is observed with MeOTf as the electrophile. This represents the first case of selective modification of the lutidine-based backbone of such noninnocent PNP ligands. Theoretical calculations support the formation of monomeric complex 2 and indicate the high reactivity of the methylene fragment in this Cu(I) complex.
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