The Et(3)N-assisted addition of beta-ketoester 3 to MVK in chloroform is catalyzed with high turnover efficiency by the phenyl-substituted uranyl-salophen compound 2b but not by the parent compound 1b. A plausible mechanism is suggested. involving concomitant nucleophilic attack at the beta-carbon and hydrogen bonding between the Et(3)NH(+) countercation and the carbonyl oxygen of the s-cis conformation of the enone reactant. The role of the van der Waals interactions with the aromatic side arm of 2b as a Crucial driving force for catalysts is discussed.
The Role of Attractive van der Waals Forces in the Catalysis of Michael Addition by a Phenyl Decorated Uranyl-Salophen Complex / DALLA CORT, Antonella; Mandolini, Luigi; Luca, Schiaffino. - In: JOURNAL OF ORGANIC CHEMISTRY. - ISSN 0022-3263. - STAMPA. - 73:23(2008), pp. 9439-9442. [10.1021/jo801714m]
The Role of Attractive van der Waals Forces in the Catalysis of Michael Addition by a Phenyl Decorated Uranyl-Salophen Complex
DALLA CORT, Antonella;MANDOLINI, Luigi;
2008
Abstract
The Et(3)N-assisted addition of beta-ketoester 3 to MVK in chloroform is catalyzed with high turnover efficiency by the phenyl-substituted uranyl-salophen compound 2b but not by the parent compound 1b. A plausible mechanism is suggested. involving concomitant nucleophilic attack at the beta-carbon and hydrogen bonding between the Et(3)NH(+) countercation and the carbonyl oxygen of the s-cis conformation of the enone reactant. The role of the van der Waals interactions with the aromatic side arm of 2b as a Crucial driving force for catalysts is discussed.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
