Nucleophilic substitution organopalladium derivatives

Tsuji, J. Palladium-catalyzed nucleophilic substitution involving allylpalladium, propargylpalladium, and related derivatives the Tsuji-Trost reaction and related carbon-carbon bond formation reactions overview of the palladium-catalyzed carbon-carbon bond formation viart-allylpalladium and propargylpalladium intermediates, in Handbook of Organopalladium Chemistry for Organic Synthesis (ed. Negishi, E.-L), 2, 1669-1687 (John Wiley Sons, New York, 2002). 

Leaving groups in the Tsuji-Trost reaction include acetates, halides, ethers, carbonates, sulfones, carbamates, epoxides, and phosphates. Reviews (a) Tsuji, J. In Handbook of Organopalladium Chemistry for Organic Synthesis, Negishi, E. deMeijere, A., Eds. Wiley-lnterscience New York, 2002 Vol II, Palladium-Catalyzed Nucleophile Substitution Involving Allyl Palladium, Propargyl-palladium and Related Derivatives, pp. 1669-1687. (b) Frost C. G. Howarth, J. Williams, J. M. J. Tetrahedron Asymmetry 1992, 3, 1089-1122. 

A novel de novo synthesis of nucleosides (Scheme 1) involves the conversion of the mwo-compound 1, derived from furan, into the pure enantiomer 2 by two successive allylations using organopalladium intermediates. The first reaction uses 6-chloropurine as nucleophile, in the presence of a chiral bisphosphine. The subsequent elaboration of 2 indicates the use of the substituted malonate as an ingenious CO2H synthon. Use of the enantiomeric catalyst in the first step gives the D-nucleoside. ... 

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