The mechanism of the Pd-catalyzed hydroarylation and hydrovinylation reaction of alkynes has been studied by a combination of experimental and theoretical methods (B3LYP), with an emphasis on the phosphine-free version. The regioselectivity of the hydroarylation and hydrovinylation shows unexpected differences, which could be attributed mainly to the higher steric demand of the cyclohexenyl group as compared to the phenyl group. Hydroarylation of alpha,beta-acetylenic carbonyl substrates yields a very unusual anti-Michael selectivity, which is shown to result from reaction of the nonconjugated double bond, leaving the conjugation intact. In all cases were the regioselectivities reproduced by the calculations.

The mechanism of the phosphine-free palladium-catalyzed hydroarylation of alkynes / Mårten, Ahlquist; Fabrizi, Giancarlo; Cacchi, Sandro; Per Ola, Norrby. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - 128:39(2006), pp. 12785-12793. [10.1021/ja061543x]

The mechanism of the phosphine-free palladium-catalyzed hydroarylation of alkynes

FABRIZI, Giancarlo;CACCHI, Sandro;
2006

Abstract

The mechanism of the Pd-catalyzed hydroarylation and hydrovinylation reaction of alkynes has been studied by a combination of experimental and theoretical methods (B3LYP), with an emphasis on the phosphine-free version. The regioselectivity of the hydroarylation and hydrovinylation shows unexpected differences, which could be attributed mainly to the higher steric demand of the cyclohexenyl group as compared to the phenyl group. Hydroarylation of alpha,beta-acetylenic carbonyl substrates yields a very unusual anti-Michael selectivity, which is shown to result from reaction of the nonconjugated double bond, leaving the conjugation intact. In all cases were the regioselectivities reproduced by the calculations.
2006
01 Pubblicazione su rivista::01a Articolo in rivista
The mechanism of the phosphine-free palladium-catalyzed hydroarylation of alkynes / Mårten, Ahlquist; Fabrizi, Giancarlo; Cacchi, Sandro; Per Ola, Norrby. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - 128:39(2006), pp. 12785-12793. [10.1021/ja061543x]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/236767
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