Chemistry  (Track)

ENANTIOSELECTIVE Pd-CATALIZED HECK ARYLATIONS USING ARENEDIAZONIUM SALTS: WHAT IS SO SPECIAL ABOUT THEM?

Carlos Roque D. Correia, Caio C. Oliveira, Juliana M. Oliveira, Ricardo A. Angnes and Rafaela C. Carmona

Chemistry Institute, State University of Campinas – UNICAMP, Campinas, 13083-970, Sao Paulo, Brazil

Abstract

The enantioselective arylation of olefins (Heck reaction) has been the subject of intense studies in the last decades because of its outstanding potential to generate new drugs, functional materials, fragrances, and other important compounds.

In this context, the palladium catalyzed coupling of arenediazonium salts to olefins (Heck-Matsuda reaction) [1] represents a robust method to access complex intermediates for the synthesis of functional and bioactive molecules. The Heck-Matsuda arylations are often milder, much faster and easier to carry out than the conventional Heck protocols. However, in spite of its many advantages and long-term existence, its enantioselective version went unreported until 2012 [2]. Its development constituted a considerable synthetic challenge mainly because of the intrinsic incompatibility between phosphine ligands and the electrophilic arenediazonium salts.

This lecture will present recent results from my laboratory to perform effective and practical asymmetric Heck-Matsuda reactions employing chiral, N,N-ligands in desymmetrization reactions [3], generation of challenging chiral tetrasubstituted tertiary centers, and quaternary stereogenic centers, together with application in the enantioselective total synthesis of drugs [4].

REFERENCES

[1] Reviews: (a) Taylor, J. G.; Moro, A. V.; Correia, C. R. D. Eur. J. Org. Chem. 2011, 1403–1428.(b) Felpin, F.-X.; Nassar-Hardy, L.; Le Callonnec, F.; Fouquet, E. Tetrahedron 2011, 67, 2815–2831.
[2] (a) Correia, C. R. D.; Oliveira, C. C.; Salles Jr. A. G.; Santos, A. F. Tetrahedron Lett. 2012, 53, 3325-3328, (b) Oliveira, C. C.; Angnes, R. A.; Correia, C. R. D. J. Org. Chem. 2013, 78, 4373-4385. (c) Werner, E. W.; Mei, T.-S.; Burckle, A. J.; Sigman, M. S. Science 2012, 338, 1455–1458.
[3] (a) Angnes, R. A.; Oliveira, J. M.; Oliveira, C. C.; Martins, N. C.; Correia, C. R. D. Chemistry – A European Journal, 2014, 20, 13117–13121, (b) Carmona, R. C.; Correia, C. R. D. Adv. Synth. Cat. 2015, 357, 2639-2643.
[4] Oliveira, C. C; Pfaltz, A.; Correia, C. R. D. C Angew. Chem Int. Ed. 2015, 54, 14036 –14039.