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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 21, 2014
A New Palladium-Catalyzed Intramolecular Allylation to Pyrrolidin-2-ones(1)
Giuliano Giambastiani1, Barbara Pacini, Marina Porcelloni
1Dipartimento di Chimica Organica "Ugo Schiff" and CNR Centro de Studio sulla Chimica e la Struttura dei Composti Eterocicli e loro Applicazioni, Via G. Capponi 9, I-50121, Firenze, Italy.
Abstract:
A novel palladium(0)-catalyzed cyclization to 3,4-disubstituted pyrrolidin-2-ones has been developed. The new approach relies upon the concomitant generation of stabilized acetamide enolate anions and of a pi-allyl-palladium appendage, properly tethered by a nitrogen atom. Reaction conditions have been optimized for the methoxycarbonyl-stabilized model reaction [(Z)-2 --> 3] and then applied to other substrates. A broad range of acetamide anion stabilizers was shown to allow the desired intramolecular C-C bond formation (MeO(2)C, MeCO, NC, (EtO)(2)PO, PhSO(2)). The cyclizations gave exclusively 5-exo-trig ring closure, thereby affording gamma-lactams. All the cyclizations gave the corresponding 3,4-disubstituted pyrrolidin-2-ones with total diastereoselection. Complete trans preference was unequivocally demonstrated for the model reaction via a NOESY experiment.
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