Image Presented A highly efficient palladium-catalyzed Heck reaction of allylic esters with arenediazonium salts is described. The reaction proceeds under mild conditions, with excellent to total regio- and stereochemical control and with retention of the traditional leaving group. Furthermore, the generality of the present methodology is illustrated by the short total synthesis of the natural kavalactones, yangonine, (±)-methysticin, and (±)-dihydromethysticin. © 2009 American Chemical Society.111636423645Beletskaya, I.P., Cheprakov, A.V., (2000) Chem. Rev, 100, p. 3009Alonso, F., Beletskaya, I.P., Yus, M., (2005) Tetrahedron, 61, p. 11771(2002) Handbook of Organopalladium Chemistry for Organic Synthesis, , Negishi, E.-I. Ed, Wiley-Interscience: New YorkTsuji, J., (2004) Palladium Reagents and Catalyst, , Wiley: Chichester, U.KCalò, V., Nacci, A., Monopoli, A., Ferola, V., (2007) J. Org. Chem, 72, p. 2596Bouquillon, S., Ganchegui, B., Estrine, B., Hénin, F., Muzart, J., (2001) J. Organomet. Chem, 634, p. 153Ambrogio, I., Cacchi, S., Fabrizi, G., Goggiamani, A., Sgalla, S., (2009) Synlett, p. 620Zawisza, A.M., Ganchegui, B., González, I., Bouquillon, S., Roglans, A., Hénin, F., Muzart, J., (2008) J. Mol. Catal. A: Chem, 283, p. 140Liu, S., Thomson, N., Pettman, A., Hyder, Z., Mo, J., Xiao, J., (2008) J. Mol. Catal. A: Chem, 279, p. 210Batt, F., Gozzi, C., Fache, F., (2008) Chem. Commun, p. 5830Scrivanti, A., Bertoldini, M., Beghetto, V., Matteoli, U., (2008) Tetrahedron, 64, p. 543Alacid, E., Nájera, C., (2007) Adv. Synth. Catal, 349, p. 2572Berthiol, F., Doucet, H., Santelli, M., (2005) Eur. J. Org. Chem, p. 1367Kang, S., Lee, H., Jang, S., Kim, T., Pyun, S., (1996) J. Org. Chem, 61, p. 2604Bernocchi, E., Cacchi, S., Ciattini, P.G., Morera, E., Ortar, G., (1992) Tetrahedron Lett, 33, p. 3073Ono, K., Fugami, K., Tanaka, S., Tamaru, Y., (1994) Tetrahedron Lett, 35, p. 4133Jeffery, T., (1991) Tetrahedron Lett, 32, p. 2121Masllorens, J., Bouquillon, S., Roglans, A., Hénin, F., Muzart, J., (2005) J. Organomet. Chem, 690, p. 3822Barbero, M., Cadamuro, S., Dughera, S., (2006) Synthesis, p. 3443Cacchi, S., Fabrizi, G., Goggiamani, A., Sferrazza, A., (2009) Synlett, p. 973Perez, R., Veronese, D., Coelho, F., Antunes, O.A.C., (2006) Tetrahedron Lett, 47, p. 1325Sengupta, S., Sadhukhan, S.K., (1998) Tetrahedron Lett, 39, p. 1237Trost, B.M., Van Vranken, D.L., (1996) Chem. Rev, 106, p. 395Pan, D., Chen, A., Su, Zhou, W., Li, S., Jia, W., Xiao, J., Jiao, N., (2008) Angew. Chem., Int. Ed, 47, p. 4729Mariampillai, B., Herse, C., Lautens, M., (2005) Org. Lett, 7, p. 4745. , For Heck arylations followed by -acetoxy elimination, see: aLautens, M., Tayama, E., Herse, C., (2005) J. Am. Chem. Soc, 127, p. 72Delcamp, J.H., White, M.C., (2006) J. Am. Chem. Soc, 128, p. 15076Su, Y., Jiao, N., (2009) Org. Lett, 11, p. 2980Aydin, J., Larsson, J.M., Selander, N., Szabó, K.J., (2009) Org. Lett, 11, p. 2852Bilia, A.R., Scalise, L., Bergonzi, M.C., Vincieri, F.F., (2004) J. Chromatogr. B, 812, p. 203Côté, C.S., Kor, C., Cohen, J., Auclair, K., (2004) Biochem. Biophys. Res. Commun, 322, p. 147Roglans, A., Pla-Quitana, A., Moreno-Manas, M., (2006) Chem. Rev, 106, p. 4622Severino, E.A., Costenaro, E.R., Garcia, A.L.L., Correia, C.R.D., (2003) Org. Lett, 5, p. 305Meira, P.R.R., Moro, A.V., Correia, C.R.D., (2007) Synthesis, p. 2279Burtoloso, A.C.B., Garcia, A.L.L., Miranda, K.C., Correia, C.R.D., (2006) Synlett, p. 3145Pastre, J.C., Correia, C.R.D., (2006) Org. Lett, 8, p. 1657da Silva, K.P., Godoi, M.N., Correia, C.R.D., (2007) Org. Lett, 9, p. 2815Gruber, A.S., Pozebon, D., Monteiro, A.L., Dupont, J., (2001) Tetrahedron Lett, 42, p. 7345. , For other Pd pre-catalysts operating under ligand-free conditions, seeMoro, A.V., Cardoso, F.S.P., Correia, C.R.D., (2008) Tetrahedron Lett, 49, p. 5668Amaral, P.A., Gouault, N., Le Roch, M., Eifler-Lima, V., David, M., (2008) Tetrahedron Lett, 49, p. 6607Hashimoto, T., Suganuma, M., Fujiki, H., Yamada, M., Kohno, T., Asakawa, Y., (2003) Phytomedicine, 10, p. 309Lygo, B., (1995) Tetrahedron, 51, p. 12859Scherer, J., (1998) Adv. Nat. Ther, 15, p. 261Bilia, A.R., Gallori, S., Vincieri, F.F., (2002) Life Sci, 70, p. 2581