Ti/Ni-Based Multimetallic System for the Efficient Allylation of Carbonyl Compounds

• Published in: European Journal of Organic Chemistry Vol. 2012; no. 8; pp. 1499 - 1503
• Main Authors: Martínez-Peragón, Ángela, Millán, Alba, Campaña, Araceli G., Rodríguez-Márquez, Irene, Resa, Sandra, Miguel, Delia, Álvarez de Cienfuegos, Luis, Cuerva, Juan M.
• Format: Book Review Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.03.2012; WILEY‐VCH Verlag; Wiley; Wiley-VCH
• Subjects: Allylation; Catalysis; Catalysts: preparations and properties; Chemistry; Chemistry, Organic; Exact sciences and technology; Free radicals chemistry; General and physical chemistry; Ketones; Nickel; Nucleophilic addition; Organic chemistry; Physical Sciences; Reactivity and mechanisms; Science & Technology; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Titanium; HALIDES; REAGENTS; Ketones; CATALYZED REDUCTIVE ALLYLATION; ALDEHYDE OXIDATION LEVEL; STRAIGHTFORWARD SYNTHESIS; Allylation; ALLYLIC ACETATES; ALCOHOL; COUPLING REACTIONS; Titanium; Nickel; ELECTROPHILES; Nucleophilic addition; Catalytic reaction; Chemical reagent; Organic carbonate; Transition metal; Ketone; Allylic compound; Carbonyl Compounds; Organic free radical; Catalyst; Room temperature; Nucleophile
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201101842

A mild method for the allylation of carbonyl compounds is presented. This methodology allows the allylation of a broad range of carbonyl compounds starting with allyl carbonates as pronucleophiles. Noteworthy is that ketones, infrequent substrates in other related protocols, are suitable substrates under these reaction conditions. Moreover, the reaction proceeds at room temperature with the use of catalytic amounts of both Ni and Ti catalysts. The success of this strategy is based on the perfect match between the late transition metal (nickel) and the radical reagent (titanium). The use of Ni instead of Pd widens the scope of this transformation and makes this method more economical. A method that uses a mixture of Ni and Ti metal catalysts was shown to be an excellent protocol for the efficient allylation of carbonyl compounds, including less reactive ketones. This method benefits from the compatibility of transition metal and free radical chemistries.