Palladium Catalyzed Heck Reaction Of Arenediazonium Tetrafluoroborate Salts With Baylis-hillman Adducts: Production Of α-benzyl-β-keto Esters

A novel experimental procedure to obtain α-benzyl-β-keto esters from the Heck reaction between arenediazonium tetrafluoroborate salts and Baylis-Hillman (BH) adducts in the presence of Pd(OAc)2 as catalyst is described. The methodology is simple, straightforward and the use of arenediazonium salts as opposed to conventional arylhalides/triflates over the usual Heck reaction is highlighted. © 2005 Elsevier Ltd. All rights reserved.47813251328Drewes, S.E., Roos, G.H.P., (1989) Tetrahedron, 44, p. 4663Basavaiah, D., Rao, A.J., Satyanarayama, T., (2003) Chem. Rev., 103, pp. 811-891Almeida, W.P., Coelho, F., (2000) Quim. Nova, 23, pp. 98-101Ciganek, E., (1997) Org. React., 51, pp. 201-350Basavaiah, D., Rao, P.D., Hyma, R.S., (1996) Tetrahedron, 52, pp. 8001-8062Santos, L.S., Pavam, C.H., Almeida, W.P., Coelho, F., Eberlin, M.N., (2004) Angew. Chem., Int. Ed., 43, pp. 4330-4333Price, K.E., Broadwater, S.J., Walker, B.J., McQuade, D.T., (2005) J. Org. Chem., 70, pp. 3980-3987Aggarwal, V.K., Fulford, S.Y., Llyod-Jones, G.C., (2005) Angew. Chem., Int. Ed., 44, pp. 1706-1708Calmès, M., Akkari, R., Barthes, N., Escale, F., Martinez, J., (2005) Tetrahedron: Asymmetry, 16, pp. 2179-2185Xue, S., He, L., Han, K.-Z., Liu, Y.-K., Guo, Q.-X., (2005) Synlett, 8, pp. 1247-1250Guo, W., Wu, W., Fan, N., Wu, Z., Xia, C., (2005) Synth. Commun., 35, pp. 1239-1251Silveira, G.P.C., Coelho, F., (2005) Tetrahedron Lett., 46, pp. 6477-6481Coelho, F., Rossi, R.C., (2002) Tetrahedron Lett., 43, pp. 2797-2800Gowrisankar, S., Lee, K.Y., Kim, J.N., (2005) Tetrahedron Lett., 46, pp. 4859-4863Coelho, F., Veronese, D., Lopes, E.C.S., Rossi, R.C., (2003) Tetrahedron Lett., 44, pp. 5731-5735Porto, R.S., Coelho, F., (2004) Synth. Commun., 34, pp. 3037-3046Porto, R.S., Vasconcellos, M.L.A.A., Ventura, E., Coelho, F., (2005) Synthesis, pp. 2297-2306Almeida, W.P., Coelho, F., (2003) Tetrahedron Lett., 44, pp. 937-940Feltrin, M.A., Almeida, W.P., (2003) Synth. Commun., 33, pp. 1141-1146Mateus, C.R., Feltrin, M.P., Costa, A.M., Coelho, F., Almeida, W.P., (2001) Tetrahedron, 57, pp. 6901-6908Iwabuchi, Y., Furukawa, M., Esumi, T., Hatakeyama, S., (2001) Chem. Commun., pp. 2030-2031Iwabuchi, Y., Sugihara, T., Esumi, T., Hatakeyama, S., (2001) Tetrahedron Lett., 42, pp. 7867-7871Masunari, A., Trazzi, G., Ishida, E., Coelho, F., Almeida, W.P., (2001) Synth. Commun., 31, pp. 2100-2109Ameer, F., Drewes, S.E., Houston-Mcmillan, M.S., Kaye, P.T., (1986) S. Afr. J. Chem., 39, pp. 57-63Hofmann, H.M.R., Rabe, J., (1984) Helv. Chim. Acta, 67, pp. 413-415Hofmann, H.M.R., Rabe, J., (1985) J. Org. Chem., 50, pp. 3849-3859Kumareswaran, R., Vankar, Y.D., (1998) Synth. Commun., 28, pp. 2291-2302Basavaiah, D., Muthukumaran, K., (1998) Tetrahedron, 54, pp. 4943-4948Sundar, N., Bhat, S.V., (1998) Synth. Commun., 28, pp. 2311-2316Kulkarni, B.A., Ganesan, A., (1999) J. Comb. Chem., 1, pp. 373-378Park, J.B., Ko, S.K., Hung, W.P., Lee, K.-J., (2004) Bull. Korean Chem. Soc., 25, pp. 927-930Navarre, L., Darses, S., Genet, J.-P., (2004) Chem. Commun., pp. 1108-1109Kabalka, G.W., Venkataiah, B., Dong, G., (2003) Org. Lett., 5, pp. 3803-3805Trost, B.M., Tsui, H.-C., Toste, F.D., (2000) J. Am. Chem. Soc., 122, pp. 3534-3535Trost, B.M., Thiel, O.R., Tsui, H.-C., (2003) J. Am. Chem. Soc., 125, pp. 13155-13164Garcia, A.L.L., Carpes, M.J.S., De Oca, A.C.B.M., Dos Santos, M.A.G., Santana, C.C., Correia, C.R.D., (2005) J. Org. Chem., 70, pp. 1050-1053Wang, C., Tan, L.-S., He, J.-P., Hu, H.-W., Xu, J.-H., (2003) Synth. Commun., 33, pp. 773-785Severino, E.A., Costenaro, E.R., Garcia, A.L.L., Correia, C.R.D., (2003) Org. Lett., 5, pp. 305-308Sengupta, S., Bhattacharyya, S., (1995) Tetrahedron Lett., 36, pp. 4475-4478Coelho, F., Almeida, W.P., Veronese, D., Mateus, C.R., Lopes, E.C.S., Silveira, G.P.C., Rossi, R.C., Pavam, C.H., (2002) Tetrahedron, 58, pp. 7437-7447Almeida, W.P., Coelho, F., (1998) Tetrahedron Lett., 39, pp. 8609-8612noteBrunner, H., Le Cousturier De Courcy, N., Genet, J.P., (1999) Tetrahedron Lett., 40, pp. 4815-4818Kozuch, S., Amatore, C., Jutand, A., Shaik, S., (2005) Organometallics, 24, p. 2319Tanaka, D., Romeril, S.P., Myers, A.G., (2005) J. Am. Chem. Soc., 127, p. 10323Sabino, A.A., MacHado, A.H.L., Correia, C.R.D., Eberlin, M.N., (2004) Angew. Chem., Int. Ed., 43, p. 2514Zeni, G., Braga, A.L., Stefani, H.A., (2003) Acc. Chem. Res., 36, p. 731Amatore, C., Jutand, A., (1999) J. Organomet. Chem., 576, p. 254Djakovitch, L., Wagner, M., Hartung, C.G., Beller, M., Koehler, K., (2004) J. Mol. Catal. A: Chem., 219, p. 121Cassol, C.C., Umpierre, A.P., MacHado, G., Wolke, S.I., Dupont, J., (2005) J. Am. Chem. Soc., 127, p. 3298Ji, Y., Jain, S., Davis, R.J., (2005) J. Phys. Chem. B, 109, p. 17232Andrews, S.P., Stepan, A.F., Tanaka, H., Ley, S.V., Smith, M.D., (2005) Adv. Synth. Catal., 347, p. 64

1,3-Butadiene hydrogenation on pd-supported systems: geometric effects

A strong metal support interaction (SMSI) effect was observed on Pd/Nb2O5 and Pd/TiO2 catalysts, and it produces small, exposed Pd ensembles. A decrease in the trans/cis 2-butene ratio was observed after reduction at 773 K. Selectivity changes were ascribed to the decoration model. Theoretical models were developed based on semi-empirical molecular-orbital calculations for 1,3-butadiene and Pd n clusters. Experimental results are in agreement with our theoretical model, which proposes a greater stabilization of the cisoid intermediate on small Pd ensembles

Catalase Vs Peroxidase Activity Of A Manganese(ll) Compound: Identification Of A Mn(iii)-(μ-o)2-mn(iv) Reaction Intermediate By Electrospray Ionization Mass Spectrometry And Electron Paramagnetic Resonance Spectroscopy

Herein, we report reactivity studies of the mononuclear water-soluble complex [Mn(II)(HPCINOL)(η1-NO3)(η2- NO3)] 1, where HPCINOL = 1-(bis-pyridin-2-ylmethyl-amino)-3- chloropropan-2-ol, toward peroxides (H2O2 and tenbutylhydroperoxide). Both the catalase (in aqueous solution) and peroxidase (in CH3CN) activities of 1 were evaluated using a range of techniques including electronic absorption spectroscopy, volumetry (kinetic studies), pH monitoring during H 2O2 disproportionation, electron paramagnetic resonance (EPR), electrospray ionization mass spectrometry in the positive ion mode [ESI(+)-MS], and gas chromatography (GC). Electrochemical studies showed that 1 can be oxidized to Mn(III) and Mn(IV). The catalase-like activity of 1 was evaluated with and without pH control. The results show that the pH decreases when the reaction is performed in unbuffered media. Furthermore, the activity of 1 is greater in buffered than in unbuffered media, demonstrating that pH influences the activity of 1 toward H2O2. For the reaction of 1 with H2O2, EPR and ESI(+)-MS have led to the identification of the intermediate [Mn(III)Mn(IV)(w-O)2(PCINOL) 2]+. The peroxidase activity of 1 was also evaluated by monitoring cyclohexane oxidation, using H2O2 or tert-butylhydroperoxide as the terminal oxidants. Low yields (<7%) were obtained for H2O2, probably because it competes with 1 for the catalase-like activity. In contrast, using tert-butylhydroperoxide, up to 29% of cyclohexane conversion was obtained. A mechanistic model for the catalase activity of 1 that incorporates the observed lag phase in O2 production, the pH variation, and the formation of a Mn(III)-(μ-O) 2-Mn(IV) intermediate is proposed. © 2009 American Chemical Society.481045694579Sies, H., (1986) Angew. Chem., 25, pp. 1058-1071Doctrow, S.R., Huffman, K., Marcus, C.B., Tocco, G., Malfroy, E., Adinolfi, C.A., Kruk, H., Malfroy, B., (2002) J. Med. Chem., 45, pp. 4549-4558Matés, J.M., (2000) Toxicology, 753, pp. 83-104Benov, L., Fridovich, I., (1998) J. Biol. Chem, 273, pp. 10313-10316Timofeevski, S.L., Nie, G., Reading, N.S., Aust, S.D., (2000) Arch. Biochem. Biophys., 373, pp. 147-153Ürek, R.Ö., Pazarlioglu, N.K., (2005) Process Biochem., 40, pp. 83-87Haschke, R.H., Friehoff, J.M., (1978) Biochem. Biophys. Res. Commun., 80, pp. 1039-1042Helliwell, B., Gutteridge, J.M.C., (1989) Free Radicals in Biology and Medicine, , Clarendon Press:Oxford, U.KKono, Y., Fridovich, I., (1983) J. Biol. Chem., 258, pp. 6015-6019Beyer Jr., W.F., Fridovich, I., (1985) Biochemistry, 24, pp. 6460-6467Barynin, V.V., Hempstead, P.D., Vagin, A.A., Antonyuk, S.V., Melik-Adamyan, W.R., Lamzin, V.S., Harrison, P.M., Artymyuk, P.J., (1997) J. Inorg. Biochem., 67, p. 196Allgood, G.S., Perry, J.J., (1986) J. Bacterid., 168, pp. 563-567Antonyuk, S.V., Melik-Adamyan, V.R., Popov, A.N., Lamzin, V.S., Hempstead, P.D., Harrison, P.M., Artmyuk, P.J., Barynin, V.V., (2000) Crystallog. Rep. (Transi. Kristallografiya), 45, pp. 105-116Barynin, V.V., Whittaker, M.M., Antonyuk, S.V., Lamzin, V.S., Harrison, P.M., Artymiuk, P.J., Whittaker, J., (2001) Structure, 9, pp. 725-738Khangulov, S.V., Barynin, V.V., Antonyuk-Barynina, S.V., (1990) Biochim. Biophys. Acta, Bioenerg., 1020, pp. 25-33Waldo, G.S., Penner-Hahn, J.E., (1995) Biochemistry, 34, pp. 1507-1512Wu, A.J., Penner-Hahn, J.E., Pecoraro, V.L., (2004) Chem. Rev., 104, pp. 903-938Mukhopadhyay, S., Mandai, S.K., Bhaduri, S., Armstrong, W.H., (2004) Chem. Rev., 104, pp. 3981-4026Dubois, L., Xiang, D.-F., Tan, X.-S., Latour, J.-M., (2005) Eur. J. Inorg. Chem., pp. 1565-1571Gelasco, A., Bensiek, S., Pecoraro, V.L., (1998) Inorg. Chem, 37, pp. 3301-3309Boelrijk, A.E.M., Dismukes, G., (1994) Biochemistry., 33, pp. 15433-15436Pecoraro, V.L., Baldwin, M.J., Gelasco, A., (1994) Chem. Rev., 94, pp. 807-826. , and references thereinBoelrijk, A.E.M., Dismukes, G.C., (2000) Inorg. Chem., 39, pp. 3020-3028Mathur, P., Crowder, M., Dismukes, G.C., (1987) J. Am. Chem. Soc., 709, pp. 5227-5233Pessiki, P.J., Khangulov, S.V., Ho, D.M., Dismukes, G.C., (1994) J. Am. Chem. Soc., 776, pp. 891-897Pessiki, P.J., Dismukes, G.C., (1994) J. Am. Chem. Soc., 776, pp. 898-903Gelasco, A., Pecoraro, V.L., (1993) J. Am. Chem. Soc., 115, pp. 7928-7929Gelasco, A., Kirk, M.L., Kampf, J.W., Pecoraro, V.L., (1997) Inorg. Chem., 36, pp. 1829-1837Sasaki, Y., Akamatsu, T., Tsuchiya, K., Ohba, S., Sakamoto, M., Nishida, Y., (1998) Polyhedron, 17, pp. 235-242Larson, E.J., Pecoraro, V.L., (1991) J. Am. Chem. Soc., 113, p. 38103818Larson, E.J., Pecoraro, V.L., (1991) J. Am. Chem. Soc., 113, pp. 7809-7810Signorella, S., Rompei, A., Buldt-Karentzopoulos, K., Krebs, B., Pecoraro, V.L., Tuchagues, J.-P., (2007) Inorg. Chem, 46, pp. 10864-10868Triller, M.U., Hsieh, W., Pecoraro, V.L., Rompei, A., Krebs, B., (2002) Inorg. Chem., 41, pp. 5544-5554Dubois, L., Pécaut, J., Carlot, M.-F., Baffert, C., Collomb, M.-N., Deronzier, A., Latour, J.-M., (2008) Chem-Eur. J., 14, pp. 3013-3025Shin, B.-K., Kim, Y., Kim, M., Han, J., (2007) Polyhedron, 26, pp. 4557-4566Biava, H., Palopoli, C., Shova, S., De Gáudio, M., Daier, V., González-Sierra, M., Tuchagues, J., Signorela, S., (2006) J. Inorg. Biochem., 700, pp. 1660-1671Dubois, L., Caspar, R., Jacquamet, L., Petit, P., Chariot, M., Baffert, C., Collomb, M., Latour, J.M., (2003) Inorg. Chem., 42, pp. 4817-4827Moreno, D., Palopoli, C., Daier, V., Shova, S., Vendier, L., Sierra, M.G., Tuchagues, J.-P., Signorella, S., (2006) Dalton Trans., pp. 5156-5166Karsten, P., Neves, A., Bortoluzzi, A.J., Strähle, J., Maichle-Mössmer, C., (2002) Inorg. Chem. Commun., 5, pp. 434-438noteFernandes, C., Parrilha, G.L., Lessa, J.A., Santiago, L.J.M., Kanashiro, M.M., Boniolo, F.S., Bortoluzzi, A.J., Horn, A., (2006) Inorg. Chim. Acta, 359, pp. 3167-3176Parrilha, G.L., Fernandes, C., Bortoluzzi, A.J., Szpoganicz, B., De Silva, M.S., Pich, C.T., Terenzi, H., Horn, A., (2008) Inorg. Chem. Commun., 11, pp. 643-647Lessa, J.A., Horn, A., Pinheiro, C.B., Farah, L.L., Eberlin, M.N., Benassi, M., Catharino, R.R., Fernandes, C., (2007) Inorg. Chem. Commun., 10, pp. 863-866Horn, A., Fernandes, C., Bortoluzzi, A.J., Vugman, N.V., Herbst, M.H.J., (2005) Mol. Struct., 749, pp. 96-102Hanson, G.R., Noble, C.J., Benson, S., (2008) Biol. Magn. Reson., 28, pp. 105-174www.octave.org, can be obtained fromGagné, R.R., Koval, C.A., Lisensky, G.C., (1980) Inorg. Chem., 19, pp. 2854-2855Esmelindro, M.C., Oestreicher, E.G., Márquez-Alvarez, H., Dariva, C., Egues, S.M.S., Fernandes, C., Bortoluzzi, A.J., Antunes, O.A.C., (2005) J. Inorg. Biochem., 99, pp. 2054-2061Whittaker, M.M., Barynin, V.V., Antonyuk, S.V., Whittaker, J.W., (1999) Biochemistry, 38, pp. 9126-9136noteGamelin, D., Kirk, M., Stemmler, T., Pal, S., Armstrong, W., Pennerhahn, J., Solomon, E., (1994) J. Am. Chem. Soc., 116, pp. 2392-2399Rush, J.D., Maskos, Z., (1990) Inorg. Chem., 29, pp. 897-905Eberlin, M.N., (2007) Eur. J. Mass Spectrom., 13, pp. 18-28Santos, L.S., Pavam, C.H., Almeida, W.P., Coelho, F., Eberlin, M.N., (2004) Angew. Chem., Int. Ed., 43, pp. 4330-4333Raminelli, C., Prechtl, M.H., Santos, G.L.S., Eberlin, M.N., Comasseto, J.V., (2004) Organometallics, 23, pp. 3990-3996Santos, L.S., Knaack, L., Metzger, J.O., (2005) Int. J. Mass Spectrom., 246, pp. 84-104Schäfer, K.O., Bittl, R., Lendzian, F., Barynin, V., Weyhermüller, T., Wieghardt, K., Lubitz, W., (2003) J. Phys. Chem. B., 107, pp. 1242-1250Wada, H., Motoda, K., Ohba, M., Sakiyama, H., Matsumoto, N., Õkawa, H., (1995) Bull. Chem. Soc. Jpn., 68, pp. 1105-1114Philouze, C., Blondín, G., Menuge, S., Auger, N., Girerd, J.-J., Vigner, D., Lance, M., Nierlich, M., (1992) Angew. Chem., Int. Ed., 31, pp. 1629-1631Pal, S., Armstrong, W.H., (1992) J. Am. Chem. Soc., 114, pp. 6398-6406Cooper, S.R., Calvin, M., (1997) J. Am. Chem. Soc., 99, pp. 6623-6630Pal, S., Armstrong, W.H., (1992) Inorg. Chem., 31, pp. 5417-5423Sarneski, J.E., Didiuk, M., Thorp, H.H., Crabtree, R.H., Brudvig, G.W., Faller, J.W., Chullte, G.K., (1991) Inorg. Chem., 30, pp. 2833-2835Pal, S., Olmstead, M.M., Armstrong, W.H., (1995) Inorg. Chem., 34, pp. 4708-4715Reddy, K.H., (2006) Bioinorganic Chemistry, , New Age International Publishers: New DelhiBoer, J.W., Browne, W.R., Feringa, B.K., Hage, R., (2007) C.R. Chim., 10, pp. 341-354Shul'pin, G.B., (2002) J. Mol. Catal. A: Chem., 789, pp. 39-66Woitiski, C.B., Kozlov, Y.N., Mandelli, D., Nizova, G.V., Schuchardt, U., Shul'pin, G.B., (2004) J. Mol. Catal. A: Chem., 222, pp. 103-119Carvalho, N.M.F., Horn, A., Antunes, O.A.C., (2006) Appl. Catal., A, 305, pp. 140-145Carvalho, N.M.F., Horn, A., Bortoluzzi, A.J., Drago, V., Antunes, O.A.C., (2006) Inorg. Chim. Acta, 359, pp. 90-98Fenton, H.J.H., (1894) J. Chem. Soc., 65, pp. 899-910Haber, F., Weiss, J., (1932) Naturwissenschaften, 57, pp. 948-95