Oxygen nucleophiles, Tsuji-Trost reaction

Acemoglu L, Williams JMJ (2002) Synthetic Scope of the Tsuji-Trost Reaction with Allylic Halides, Carboxylates, Ethers, and Related Oxygen Nucleophiles as Starting Compounds. In Negishi E, de Meijere A (eds) Handbook of Organopalladium Chemistry for Organic Synthesis. Wiley, New York, p 1689... 

V.2.1.2 Synthetic Scope of the Tsuji-Trost Reaction with Allylic Halides, Carboxylates, Ethers, and Related Oxygen Nucleophiles as Starting Compounds... 

While the reaction of aliphatic alcohols can be problematic, there are several examples reported in the synthesis of complex molecular targets. For example, the use of Tsuji-Trost reaction in the synthesis of cis-2,5-disubstituted tetrahydrofiirans was reported by Williams and co-workers. They used a soft oxygen nucleophile in an intramolecular reaction to prepare the C7-C22 core of amphidinolide K 45. It was found the addition of MesSnCl was necessary to both suppress acyl migration and ensure the oxygen was strongly nucleophilic. 

The Tsuji-Trost reaction is the palladinum-catalyzed substitution of allylic leaving groups by carbon nucleophiles. The nucleophile can be carbon-, nitrogen-, or oxygen- based compounds such as alcohols, enolates, phenols, and enamines, and the leaving group can be a halide or an acetate. This emerged as a powerful procedure for the formation of C—C, C—O and C—N bonds. The reaction, also known as Trost allylation or allylic alkylation, was named after Jiro Tsuij, who first reported the method in 1965 [42], and Barry Trost, who introduced an asymmetric version in 1973 [43]. 

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