Allylic substitution mediated by water and palladium: Unusual role of a palladium(II) catalyst and ESI-MS analysis

Carole Chevrin, Jean Le Bras, Françoise Hénin, Jacques Muzart, Anna Pla-Quintana, Anna Roglans, Roser Pleixats

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47 Citations (Scopus)

Abstract

Allylic substitution of PhCH(OAc)CH=CHPh by CH2(COMe) 2 in a basic MeOH/H2O mixture could be achieved in the absence of a palladium catalyst and lead to a mixture of PhCH(CH(COMe) 2)CH=CHPh and PhCH(OMe)CH=CHPh in 40% and 55% yields, respectively. The process is induced by water, and nucleophilic attack addition occurred on a stabilized carbocation as the intermediate. Addition of a catalytic amount of PdCl2(CH3CN)2 did not accelerate the reaction but improved the selectivity, and PhCH(CH(COMe)2)CH=CHPh was then obtained in 92% yield while PhCH(OMe)-CH=CHPh was observed in trace amounts. An ESI-MS analysis of the reaction mixture led us to assume that a palladium acetylacetonate complex is involved in the formation of PhCH(CH(COMe) 2)CH=CHPh.
Original languageEnglish
Pages (from-to)4796-4799
JournalOrganometallics
Volume23
Issue number20
DOIs
Publication statusPublished - 27 Sep 2004

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