Intermolecular Enantioselective Heck-matsuda Arylations Of Acyclic Olefins: Application To The Synthesis Of β-aryl-γ-lactones And β-aryl Aldehydes

We describe herein a synthetically useful method for the enantioselective intermolecular Heck-Matsuda arylation of acyclic allylic alcohols. Aryldiazonium tetrafluoroborates were applied as arylating agents in the presence of Pd(TFA)2 and a chiral, commercially available, bisoxazoline ligand. The methodology is straightforward, robust, scalable up to a few grams, and of broad scope allowing the synthesis of a range of β-aryl-carbonyl compounds in good to high enantioselectivities and yields. This new enantioselective Heck-Matsuda arylation allowed the synthesis of β-aryl-γ-lactones and β-aryl aldehydes, which play a vital role as key intermediates in the synthesis of the biologically active compounds, such as (R)-baclofen, (R)-rolipram, (S)-curcumene, (S)-dehydrocurcumene, and (S)-tumerone. © 2013 American Chemical Society.78943734385Ozawa, F., Kubo, A., Hayashi, T., (1991) J. Am. Chem. Soc., 113, pp. 1417-1419Cartney, D.M., Guiry, P.J., (2011) Chem. Soc. Rev., 40, pp. 5122-5150Coeffard, V., Guiry, P.J., (2010) Curr. Org. Chem., 14, pp. 212-229Dounay, A.B., Overman, L.E., (2003) Chem. Rev., 103, pp. 2945-2964Yang, Z., Zhou, J., (2012) J. Am. Chem. Soc., 134, pp. 11833-11835Zhao, L., Li, Z., Chang, L., Xu, J., Yao, H., Wu, X., (2012) Org. Lett., 14, pp. 2066-2069Gao, P., Cook, S.P., (2012) Org. Lett., 14, pp. 3340-3343Gøgsig, T.M., Kleimark, J., Nilsson Lill, S.O., Korsager, S., Lindhardt, A.T., Norrby, P.-O., Skrydstrup, T., (2012) J. Am. Chem. Soc., 134, pp. 443-452Shard, A., Sharma, N., Bharti, R., Dadhwal, S., Kumar, R., Sinha, A.K., (2012) Angew. Chem., Int. Ed., 51, pp. 12250-12253Gottumukkala, A.L., De Vries, J.G., Minnaard, A.J., (2011) Chem. - Eur. J., 17, pp. 3091-3095Oestreich, M., (2009) The Mizoroki-Heck Reaction, , Ed. Wiley: Chichester, UKKoga, Y., Sodeoka, M., Shibasaki, M., (1994) Tetrahedron Lett., 35, pp. 1227-1230Yonehara, K., Mori, K., Hashizume, T., Chung, K.-G., Ohe, K., Uemura, S., (2000) J. Organomet. Chem., 603, pp. 40-49Werner, E.W., Mei, T.-S., Burckle, A.J., Sigman, M.S., (2012) Science, 338, pp. 1455-1458. , When this manuscript was in preparation, Sigman et al. reported the Heck-Matsuda arylation of acyclic alkenyl alcohols using a strategy similar to oursCorreia, C.R.D., Oliveira, C.C., Salles Jr., A.G., Dos Santos, E.A.F., (2012) Tetrahedron Lett., 53, pp. 3325-3328Roglans, A., Pla-Quintana, A., Moreno-Manas, M., (2006) Chem. Rev., 106, pp. 4622-4643Taylor, J.G., Moro, A.V., Correia, C.R.D., (2011) Eur. J. Org. Chem., pp. 1403-1428Felpin, F.-X., Nassar-Hardy, L., Le Callonnec, F., Fouquet, E., (2011) Tetrahedron, 67, pp. 2815-2831Barancelli, D.A., Salles, A.G., Taylor, J.G., Correia, C.R.D., (2012) Org. Lett., 14, pp. 6036-6039Oliveira, C.C., Dos Santos, E.A.F., Nunes, J.H.B., Correia, C.R.D., (2012) J. Org. Chem., 77, pp. 8182-8190Soldi, C., Moro, A.V., Pizzolatti, M.G., Correia, C.R.D., (2012) Eur. J. Org. Chem., pp. 3607-3616Moro, A.V., Rodrigues Dos Santos, M., Correia, C.R.D., (2011) Eur. J. Org. Chem., pp. 7259-7270Werner, E.W., Sigman, M.S., (2011) J. Am. Chem. Soc., 133, pp. 9692-9695Schmidt, B., Hölter, F., Kelling, A., Schilde, U., (2011) J. Org. Chem., 76, pp. 3357-3365Cacchi, S., Fabrizi, G., Goggiamani, A., Sferrazza, A., (2011) Org. Biomol. Chem., 9, pp. 1727-1730Prediger, P., Barbosa, L.F., Génisson, Y., Correia, C.R.D., (2011) J. Org. Chem., 76, pp. 7737-7749Callonnec, F.L., Fouquet, E., Felpin, F.-X., (2011) Org. Lett., 13, pp. 2646-2649Susperregui, N., Miqueu, K., Sotiropoulos, J.-M., Le Callonnec, F., Fouquet, E., Felpin, F.-X., (2012) Chem. - Eur. J., 18, pp. 7210-7218Felpin, F.-X., Miqueu, K., Sotiropoulos, J.-M., Fouquet, E., Ibarguren, O., Laudien, J., (2010) Chem. - Eur. J., 16, pp. 5191-5204Sabino, A.A., MacHado, A.H.L., Correia, C.R.D., Eberlin, M.N., (2004) Angew. Chem., Int. Ed., 43, pp. 2514-2518(2004) Angew. Chem., Int. Ed., 43, p. 4389Vogt, M., Ceylan, S., Kirschning, A., (2010) Tetrahedron, 66, pp. 6450-6456. , Dibenzilidene-acetone (dba) impurities are sometimes difficult to remove, requiring a reduction step before purification of the reaction products. For an example, seeTundo, P., Selva, M., (2002) Acc. Chem. Res., 35, pp. 706-716Arcadi, A., Bernocchi, E., Cacchi, S., Marinelli, F., (1991) Tetrahedron, 47, pp. 1525-1540Cacchi, S., Fabrizi, G., Goggiamani, A., Sferrazza, A., (2009) Synlett, pp. 973-977Zhou, L., Liu, X., Ji, J., Zhang, Y., Hu, X., Lin, L., Feng, X., (2012) J. Am. Chem. Soc., 134, pp. 17023-17026Petersen, K.S., Stoltz, B.M., (2011) Tetrahedron, 67, pp. 4352-4357Xu, S., Wang, Z., Zhang, X., Zhang, X., Ding, K., (2008) Angew. Chem., Int. Ed., 47, pp. 2840-2843Brenna, E., Caraccia, N., Fuganti, C., Fuganti, D., Grasselli, P., (1997) Tetrahedron: Asymmetry, 8, pp. 3801-3805Braun, M., Unger, C., Opdenbusch, K., (1998) Eur. J. Org. Chem., pp. 2389-2396Honda, T., Ishikawa, F., Kanai, K., Sato, S., Kato, D., Tominaga, H., (1996) Heterocycles, 42, pp. 109-112Csizmadiová, J., Mečiarová, M., Rakovský, E., Horváth, B., Šebesta, R., (2011) Eur. J. Org. Chem., pp. 6110-6116Berhal, F., Wu, Z., Genet, J.-P., Ayad, T., Ratovelomanana-Vidal, V., (2011) J. Org. Chem., 76, pp. 6320-6326Gendrineau, T., Chuzel, O., Eijsberg, H., Genet, J.-P., Darses, S., (2008) Angew. Chem., Int. Ed., 47, pp. 7669-7672Chung, Y.-C., Janmanchi, D., Wu, H.-L., (2012) Org. Lett., 14, pp. 2766-2769Čorić, I., Müller, S., List, B., (2010) J. Am. Chem. Soc., 132, pp. 17370-17373Felice, V.D., De Renzi, A., Fraldi, N., Panunzi, B., (2009) Inorg. Chim. Acta, 362, pp. 2015-2019Calò, V., Nacci, A., Monopoli, A., Ferola, V., (2007) J. Org. Chem., 72, pp. 2596-2601Afewerki, S., Breistein, P., Pirttilä, K., Deiana, L., Dziedzic, P., Ibrahem, I., Córdova, A., (2011) Chem. - Eur. J., 17, pp. 8784-8788Bräse, S., Höfener, S., (2005) Angew. Chem., Int. Ed., 44, pp. 7879-7881Stivala, C.E., Zakarian, A., (2011) J. Am. Chem. Soc., 133, pp. 11936-11939Xu, H.-J., Zhu, F.-F., Shen, Y.-Y., Wan, X., Feng, Y.-S., (2012) Tetrahedron, 68, pp. 4145-4151Malkov, A.V., Friscourt, F., Bell, M., Swarbrick, M.E., Kočovský, P., (2008) J. Org. Chem., 73, pp. 3996-4003Kotsuki, H., Shinohara, T., Fujioka, S., (2001) Heterocycles, 55, pp. 237-242Kim, S.-G., (2008) Tetrahedron Lett., 49, pp. 6148-6151Akagawa, K., Akabane, H., Sakamoto, S., Kudo, K., (2008) Org. Lett., 10, pp. 2035-203

Stereoselective Synthesis Of Aryl Cyclopentene Scaffolds By Heck-matsuda Desymmetrization Of 3-cyclopentenol

A new enantioselective Heck-Matsuda desymmetrization reaction was accomplished by using 3-cyclopentenol to produce chiral five-membered 4-aryl cyclopentenol scaffolds in good yields and high ee's, together with some 3-aryl-cyclopentanones as minor products. Mechanistically, the hydroxyl group of 3-cyclopentenol acts as a directing group and is responsible for the cis- arrangement in the formation of the 4-aryl-cyclopentenols.20411311713121Sun, C., Potter, B., Morken, J.P., (2014) J. Am. Chem. Soc., 136, pp. 6534-6537Chen, X., Xiong, F., Chen, W., He, Q., Chen, F., (2014) J. Org. Chem., 79, pp. 2723-2728Tay, D.W., Leung, G.Y.C., Yeung, Y.-Y., (2014) Angew. Chem., 126, pp. 5261-5264(2014) Angew. Chem. Int. Ed., 53, pp. 5161-5164Rong, Z.-Q., Pan, H.-J., Yan, H.-L., Zhao, Y., (2014) Org. Lett., 16, pp. 208-211Roux, C., Candy, M., Pons, J.-M., Chuzel, O., Bressy, C., (2014) Angew. Chem., 126, pp. 785-789(2014) Angew. Chem. Int. Ed., 53, pp. 766-770García-Urdiales, E., Alfonso, I., Gotor, V., (2011) Chem. Rev., 111, pp. 110-180Yang, W., Yan, J., Long, Y., Zhang, S., Liu, J., Zeng, Y., Cai, Q., (2013) Org. Lett., 15, pp. 6022-6025Chu, L., Wang, X.-C., Moore, C.E., Rheingold, A.L., Yu, J.-Q., (2013) J. Am. Chem. Soc., 135, pp. 16344-16347Shibasaki, M., Ohshima, T., (2009) The Mizoroki-Heck Reaction, pp. 463-483. , (Ed.: M. Oestreich), John Wiley & Sons, ChichesterRoglans, A., Pla-Quintana, A., Moreno-Mañas, M., (2006) Chem. Rev., 106, pp. 4622-4643Taylor, J.G., Moro, A.V., Correia, C.R.D., (2011) Eur. J. Org. Chem., 2011, pp. 1403-1428Felpin, F.-X., Nassar-Hardy, L., Lecallonnec, F., Fouquet, E., (2011) Tetrahedron, 67, pp. 2815-2831Oestreich, M., (2014) Angew. Chem., 126, pp. 2314-2317(2014) Angew. Chem. Int. Ed., 53, pp. 2282-2285Prediger, P., Silva, A.R.D., Correia, C.R.D., (2014) Tetrahedron, 70, pp. 3333-3341Oger, N., Lecallonnec, F., Jacquemin, D., Fouquet, E., Legrognec, E., Felpin, F.X., (2014) Adv. Synth. Catal., 356, pp. 1065-1071Schmidt, B., Berger, R., (2013) Adv. Synth. Catal., 355, pp. 463-476Elbakouri, O., Fernández, M., Brun, S., Pla-Quintana, A., Roglans, A., (2013) Tetrahedron, 69, pp. 9761-9765Kawagishi, F., Toma, T., Inui, T., Yokoshima, S., Fukuyama, T., (2013) J. Am. Chem. Soc., 135, pp. 13684-13687Schmidt, B., Elizarov, N., Berger, R., Hölter, F., (2013) Org. Biomol. Chem., 11, pp. 3674-3691Correia, C.R.D., Oliveira, C.C., Salles, A.G., Jr., Santos, E.A.F., (2012) Tetrahedron Lett., 53, pp. 3325-3328Oliveira, C.C., Angnes, R.A., Correia, C.R.D., (2013) J. Org. Chem., 78, pp. 4373-4385Werner, E.W., Mei, T.-S., Burckle, A.J., Sigman, M.S., (2012) Science, 338, pp. 1455-1458Heasley, B., (2014) Curr. Org. Chem., 18, pp. 641-686Kobayashi, Y., Nakata, K., Ainai, T., (2005) Org. Lett., 7, pp. 183-186Liu, S., Zhou, J., (2013) Chem. Commun., 49, pp. 11758-11760Xu, L., Hilton, M.J., Zhang, X., Norrby, P.-O., Wu, Y.-D., Sigman, M.S., Wiest, O., (2014) J. Am. Chem. Soc., 136, pp. 1960-1967Dang, Y., Qu, S., Wang, Z.-X., Wang, X., (2014) J. Am. Chem. Soc., 136, pp. 986-998Oliveira, C.C., Dossantos, E.A.F., Nunes, J.H.B., Correia, C.R.D., (2012) J. Org. Chem., 77, pp. 8182-8190Huang, L., Qi, J., Wu, X., Huang, K., Jiang, H., (2013) Org. Lett., 15, pp. 2330-2333Smadja, W., Czernecki, S., Ville, G., Georgoulis, C., (1987) Organometallics, 6, pp. 166-169Eshthiaghhosseini, H., Beyramabadi, S., Morsali, A., Housaindokht, M.R., (2010) J. Mol. Struct., 941, pp. 138-143Keith, J.A., Oxgaard, J., Goddard, W.A., III, (2006) J. Am. Chem. Soc., 128, pp. 3132-3133Berhal, F., Wu, Z., Genet, J.-P., Ayad, T., Ratovelomanana-Vidal, V., (2011) J. Org. Chem., 76, pp. 6320-6326Csizmadiová, J., Mečiarová, M., Rakovský, E., Horváth, B., Šebesta, R., (2011) Eur. J. Org. Chem., pp. 6110-6116Gendrineau, T., Chuzel, O., Eijsberg, H., Genet, J.-P., Darses, S., (2008) Angew. Chem., 120, pp. 7783-7786(2008) Angew. Chem. Int. Ed., 47, pp. 7669-767