Ethers organopalladium derivatives

B.iii. Organopalladium Derivatives Generated from Allyl Esters and Ethers... 

Ito, Y., Suginome, M. Palladium-catalyzed or -promoted oxidation via 1,2- or 1,4-elimination oxidation of silyl enol ethers and related enol derivatives to a,P-unsaturated enones and other carbonyl compounds. Handbook of Organopalladium Chemistry for Organic Synthesis 2002, 2, 2873-2879. 

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. 

Kickham, J.E. Loeb, S.J. Simultaneous first- and seeond-sphere coordination. Organopalladium crown ether eom-plexes as metalloreeeptors for o-aminopyridine derivatives. Inorg. Chem. 1994, 33, 4351-4359. 

The complexity of this reaction scheme already points out the necessary time-balance between oxidative addition, CO insertion versus deinsertion (decarbonylation), acylpalladation, carbopaUadation, and dehydropalladation events to have a selective acylpallada-tion-type reaction. This has been more recently addressed by selecting acyl chlorides that could not readily undergo dehydropalladation, hence stabilizing the organopalladium intermediates to favor their intramolecular reaction with alkenes. For instance, Pd(OAc)2 catalyzes the reaction of benzoyl chloride derivatives with enol ethers (R = OEt, Scheme 3) to give the corresponding acylpalladation products typically in 40-77% yields. " ... 

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