Abstract
When stoichiometric π-complexes are used in asymmetric synthesis, the metal centre can be brought into play in a series of reactions. In this way, the most efficient use is made of the metal/ligand system. In contrast, if asymmetric control is required at just a single synthetic step, the best way to proceed is to use a chiral catalyst system, so that only a small amount of the often expensive chiral auxiliary is then needed. However when catalytic control methods must operate in a series of separate reactions, the approach relies, at each step, on a new and highly selective recognition of an increasingly elaborate chiral substrate. After the first induction of asymmetry, subsequent asymmetric induction is diastereoselective, not enantioselective.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
McQuillin, F.J., Parker, D.G. and Stephenson, G.R., Transition Metal Organometallics for Organic Synthesis,Chs 7 and 14, Cambridge University Press, Cambridge, 1991; (b) Stephenson, G.R., Alexander, R.P., Morley, C. and Howard, P.W., Philos. Trans. R. Soc. bond., A,1988, 326,545.
Davies, S.G, Green, M.L.H. and Mingos, D.M.P., Tetrahedron, 1978, 34, 3047.
Birch, A.J., Ratnayake Bandara, B.M., Chamberlain, K., Chauncy, B., Dahler, P., Day, A.I, Jenkins, I.D., Kelly, L.F, Khor, T.-C, Kretschmer, G, Liepa, A.J, Narula, A.S, Raverty, W.D, Rizzardo, E, Sell, C, Stephenson, G.R., Thompson, D. J. and Williamson, D.H., Tetrahedron, 1981, 37, 289.
Birch, A. J. and Bandara, B.M.R, Tetrahedron Lett., 1980, 2981.
Chang, T.C.T, Coolbaugh, T.S, Foxman, B.M, Rosenblum, M, Simms, N. and Stockmann, C, Organometallics, 1987, 6, 2394.
Chu, K.-H, Zhen, W, Zhu, X.-Y. and Rosenblum, M, Tetrahedron Lett., 1992, 33, 1173.
Enders, D. and Finkam, M, Synlett, 1993, 401.
Koot, W.-J, Hiemstra, H. and Speckamp, W.N, J. Chem. Soc, Chem. Commun., 1993, 156.
Pearson, A.J. and Khan, M.N.I, J. Am. Chem. Soc., 1984, 106, 1872.
Pearson, A.J, Khan, M.N.I, Clardy, J.C. and Cun-Heng, H, J. Am. Chem. Soc., 1985, 107, 2748; (b) Pearson, A. J. and Khan, M.N.I, J. Org. Chem.,1985, 50, 5276.
Faller, J.W., Murray, H.H., White, D.L. and Chao, K.H., Organometallics, 1983, 2, 400.
Pearson, A.J., Blystone, S.L., Nar, H., Pinkerton, A.A., Roden, B.A. and Yoon, J., J. Am. Chem. Soc., 1989, 111, 134.
Vong, W.-J., Peng, S.-M., Lin, S.-H., Lin, W.-J. and Liu, R.-S., J. Am. Chem. Soc., 1991, 113, 573.
Cheng, M.-H., Ho, Y.-H., Lee, G.-H., Peng, S.-M. and Liu, R.-S., J. Chem. Soc, Chem. Commun., 1991, 697.
Stephenson, G.R., Astley, S.T., Palotai, I.M., Howard, P.W., Owen, D.A. and Williams, S., Organic Synthesis via Organometallics, in K.H. Dötz and R.W. Hoffmann (eds), Vieweg, Braunschweig, 1991, p. 169.
Alton, J.G., Evans, DJ., Kane-Maguire, L.A.P. and Stephenson, G.R., J. Chem. Soc, Chem. Commun., 1984, 1246.
Birch, A.J., Rafferty, W.D. and Stephenson, G.R., Organometallics, 1984, 3, 1075.
Stephenson, G.R., Aust. J. Chem., 1981, 34, 2339.
Kelly, L.F., Narula, A.S. and Birch, A.J., Tetrahedron Lett., 1980, 2455; (b) Birch, A.J., Dahler, P., Narula, A.S. and Stephenson, G.R., Tetrahedron Lett.,1980, 3817; (?) Pearson, A. J. and Raithby, P.R, J. Chem. Soc, Perkin Trans. 1,1980, 395.
Birch, A.J. and Stephenson, G.R., Tetrahedron Lett., 1981, 22, 779.
For a discussion of a-and co-directing effects, see Ref. 15 and Ref. 2, pp. 2-7. In discussion of regiocontrol, ipso (i) indicates addition at the atom carrying the substitutent, α indicates addition adjacent to this position, and ωindicates addition at the end of the π-system most distant from the substituent.
Pearson, A.J. and O’Brien, M.K., J. Org. Chem., 1989, 54, 4663.
Bandara, B.M.R., Birch, A.J. and Kelly, L.F., J. Org. Chem., 1984, 49, 2496.
Birch, A.J., Raverty, W.D. and Stephenson, G.R., J. Chem. Soc, Chem. Commun., 1980, 857.
Birch, A.J., Kelly, L.F. and Weerasuria, D.V., J. Org. Chem., 1988, 53, 278.
Stephenson, G.R., Owen, D.A., Finch, H. and Swanson, S., Tetrahedron Lett., 1990, 31, 3401.
Birch, A.J, Cross, P.E., Lewis, J, White, D.A. and Wild, S.B., J. Chem. Soc, A, 1968, 332.
Birch, A.J., Kelly, L.F. and Thompson, D.J., J. Chem. Soc, Perkin Trans. 1, 1981, 1006.
Mincione, F., Bovicelli, P., Carrini, S. and Lamba, D., Heterocycles, 1985, 23, 1607.
Stephenson, G.R., Owen, D.A., Finch, H. and Swanson, S., Tetrahedron, 1993, 25, 5649.
Stephenson, G.R., Howard, P.W. and Taylor, S.C., J. Organomet. Chem., 1989, 370, 97.
Astley, ST., Meyer, M. and Stephenson, G.R., Tetrahedron Lett., 1993, 34, 2035.
Astley, S.T. and Stephenson, G.R., Synlett, 1992, 507.
Pearson, A.J., Kole, S.J. and Ray, T., J. Am. Chem. Soc., 1984, 106, 6060.
Pearson, A.J., Lai, Y.-S., Lu, W. and Pinkerton, A.A., J. Org. Chem., 1989, 54, 3882.
Pearson, A.J, Lai, Y.-S. and Srinivasan, K, Aust. J. Chem., 1992, 45, 109.
Pearson, A.J, Balasubramaniam, S. and Srinivasan, K, Tetrahedron, 1993, 49, 5663.
Potter, G.A. and McCague, R, J. Chem. Soc, Chem. Commun., 1990, 1172.
Potter, G.A. and McCagne, R, J. Chem. Soc, Chem. Commun., 1992, 635.
Pearson, A.J. and Richards, I.C, J. Organometal. Chem., 1983, 258, C41.
Semmelhack, M.F, Clark, G.R, Garcia, J.L, Harrison, J.J, Thebtaranonth, Y, Wulff, W. and Yamashita, A, Tetrahedron, 1981, 37, 3957.
Chung, Y.K, Willard, P.G. and Sweigart, D.A, Organometallics, 1982, 1, 1053; Honig, E.D. and Sweigart, D.A, J. Chem. Soc, Chem. Commun.,1986, 691.
Honig, E.D. and Sweigart, D.A, J. Chem. Soc, Chem. Commun., 1986, 691.
Alexakis, A, Mangeney, P, Marck, I, Rose-Munch, F, Rose, E, Semra, A. and Robert, F, J. Am. Chem. Soc., 1992, 114, 8289.
Davies, S.G. and Goodfellow, C.L, J. Chem. Soc, Perkin Trans. 1, 1990, 393; (b) Bromley, L.A., Davies, S.G. and Goodfellow, C.L, Tetrahedron: Asymmetry,1991, 2, 139.
Kondo, Y, Green, J.R. and Ho, J, J. Org. Chem., 1993, 58, 6182.
Solladié-Cavallo, A, Solladié, G. and Tsamo, E.J, J. Org. Chem., 1979, 4, 4189; (b) Solladié-Cavallo, A. and Suffert, J, Magn. Reson. Chem.,1985, 23,739.
Uemura, M, Miyake, R, Nakayama, K, Shiro, M. and Hayashi, Y, J. Org. Chem., 1993, 58, 1238.
Yamazaki, Y. and Kobayashi, H, Tetrahedron: Asymmetry, 1993, 4, 1287; (b) Howell, J.A.S, Palin, M.G., Jaouen, G, Top, S, El Hafa, H. and Cense, J.M, Tetrahedron: Asymmetry,1993, 4, 1241.
Kündig, E.P., Liu, R. and Ripa, A., Heb. Chim. Acta., 1992, 75, 2657.
Saha, M. and Nicholas, K.M., J. Org. Chem., 1984, 49, 47; (b) Nicholas, K.M., Ace. Chem Res.,1987, 20,207.
Ganesh, P. and Nicholas, K.M., J. Org. Chem., 1993, 58, 5587.
Jacobi, P.A. and Zheng, W., Tetrahedron Lett., 1993, 34, 2581; (b) Jacobi, P.A. and Zheng, W., Tetrahedron Lett.,1993, 34, 2585.
Bradley, D.H., Khan, M.A. and Nicholas, K.M., Organometallies, 1992, 11, 2598.
Caffyn, A.J.M. and Nicholas, K.M., J. Am. Chem. Soc., 1993, 115, 6438.
Magnus, P. and Fortt, S.M., J. Chem. Soc, Chem. Commun., 1991, 44; (b) Maier, M.E. and Brandstetter, T., Tetrahedron Lett.,1991, 32,3679.
Magnus, P. and Pitterna, T., J. Chem. Soc, Chem. Commun., 1991, 541.
Magnus, P. and Davies, M., J. Chem. Soc, Chem. Commun., 1991, 1522.
Lin, S.-H., Cheng, W.-J., Liao, Y.-L., Wang, S.-L., Lee, G.-H, Peng, S.-M. and Liu, R.-S., J. Chem. Soc, Chem. Commun., 1993, 1391.
Franck-Neumann, M., Pure Appl. Chem., 1983, 55, 1715; (b) Monpert, A, Martelli, J, Grée, R. and Carrie, R., Nouveau J. Chim.,1983, 7, 345; (c) Franck-Neumann, M., Martina, D. and Heitz, M.P, Tetrahedron Lett.,1982, 3493; (c) Monpert, A, Martelli, J., Grée, R. and Carrie, R, Tetrahedron Lett.,1981, 22,1961.
Donaldson, W.A. and Tao, C, Synlett, 1991, 895.
Tao, C. and Donaldson, W.A., J. Org. Chem., 1993, 58, 2134.
Monpert, A., Martelli, J., Grée, R. and Carrie, R., Tetrahedron Lett., 1981, 22, 1961.
Franck-Neumann, M. and Colson, P.-J., Synlett, 1991, 891.
Nunn, K, Mosset, P., Grée, R. and Saalfrank, R.W, Angew. Chem., Int. Ed. Engl., 1988, 27, 1188.
Nunn, K., Mosset, P, Grée, R. and Saalfrank, R.W, J. Org. Chem., 1992, 57, 3359.
Gigou, A, Beaucourt, J.-P, Lellouche, J.-P. and Grée, R, Tetrahedron Lett., 1991, 32, 635.
Colonna, S, Manfredi, A, Solladié-Cavallo, A. and Quazzotti, S, Tetrahedron Lett., 1990, 31, 6185.
Mukai, C, Kim, I.J. and Hanoaka, M, Tetrahedron: Asymmetry, 1992, 3, 1007.
Mukai, C, Kim, I.J. and Hanoaka, M, Tetrahedron Lett., 1993, 34, 6081.
Uemura, M, Minami, T, Shiro, M. and Hayashi, Y, J. Org. Chem., 1992, 57, 5590.
Ganesh, S. and Sarkar, A, Tetrahedron Lett., 1991, 8, 1085.
Reetz, M.T. and Sauerwald, M, Tetrahedron Lett., 1983, 24, 2837.
Brocard, J, Lebibi, J. and Couturier, D, J. Chem. Soc, Chem. Commun., 1981, 1264.
Joauen, G, Top, S, Laconi, A, Couturier, D. and Brocard, J, J. Am. Chem. Soc., 1984, 106, 2207.
Blagg, J, Davies, S.S., Holman, N.J., Laughton, C.A. and Mobbs, B.E., J. Chem. Soc, Perkin Trans. 1, 1986, 1581.
Moriarty, R.M., Engerer, S.G, Prakash, O, Prakash, I, Gill, U.S. and Freeman, W.A, J. Chem. Soc, Chem. Commun., 1985, 1715.
Uemura, M, Nishimura, H, Minami, T. and Hayashi, Y, J. Am. Chem. Soc., 1991, 113, 5402.
Schmailz, H.-G, Hollander, J, Arnold, M. and Durner, G, Tetrahedron Lett., 1993, 34, 6259.
Agoston, G.E, Cabal, M.P. and Turos, E, Tetrahedron Lett., 1991, 32, 3001.
Faller, J.W, Nguyen, J.T, Ellis, W. and Mazzieri, M.R, Organometallics, 1993, 12, 1434.
Cheng, M.-H, Ho, Y.-H, Wang, S.-L, Cheng, C.-Y, Peng, S.-M, Lee, G.-H. and Liu, R.-S, J. Chem. Soc, Chem. Commun., 1992, 45.
Pearson, A. J. and Srinavasan, K, Tetrahedron Lett., 1992, 33, 7295.
Schmeck, C. and Hegedus, L.S, J. Am. Chem. Soc., 1994, 116, 9927.
Aumann, R, J. Organometal. Chem., 1973, 47, C29.
Aumann, R, Fröhlich, K. and Ring, H, Angew. Chem., Int. Ed. Engl., 1974, 13, 275; (b) Aumann, R, Ring, H, Krüger, ?. and Goddard, R, Chem. Ber.,1979, 112,3644; (c) Annis, G.D. and Ley, S.V., J. Chem. Soc, Chem. Commun.,1977, 581.
Ley, S.V., Philos. Trans. R. Lond. A, 1988, 326, 633.
Kotecha, N.R, Ley, S.V. and Mantegani, S, Synlett, 1992, 395.
Knölker, H.-J, Heber, J. and Mahler, C.H, Synlett, 1992, 1002.
Pearson, A.J, Shirley, R.J. Jr and Dubbert, R.A, Organometallics, 1992, 11, 4096; (b) Pearson, A. J. and Shirley, R. J. Jr Organometallics,1994, 13,578.
Sternberg, E.D. and Vollhardt, K.P.C, J. Org. Chem., 1984, 49, 1564; (b) Boese, R, Rodriguez, J. and Vollhardt, K.P.C, Angew. Chem., Int. Ed. Engl., 1991, 30,993.
Semmelhack, M.F., Tamura, R., Schnatter, W. and Springer, J., J. Am. Chem. Soc., 1984, 106, 5363.
Semmelhack, M.F. and Park, J, J. Am. Chem. Soc., 1987, 109, 935.
Chamberlain, S. and Wulff, W.D, J. Am. Chem. Soc., 1992, 114, 10667.
Schreiber, S.L, Sammakia, T. and Crowe, W.E., J. Am. Chem. Soc., 1986, 108, 3128.
Bernardes, V., Verdaguer, X, Kardos, N., Riera, A., Moyano, A., Pericas, M.A. and Greene, A.E., Tetrahedron Lett., 1994, 35, 575.
Wakefield, J.B. and Stryker, J.M., J. Am. Chem. Soc., 1991, 113, 7057; (b) Carfagna, C, Galarini, R., Musco, A. and Santi, R., Organometallics, 1991, 10,3956.
Semmelhack, M.F., Herndon, J.W, Organometallics, 1983, 2, 363; (b) Semmelhack, M.F, Herndon, J.W. and Springer, J.P, J. Am. Chem. Soc, 1983, 105,2497; (c) Yeh, M.-C. and Hwu, C.-C, J. Organometal. Chem.,1991, 419,341; (d) Yeh, M.-C.P, Sheu, B.-A, Fu, H.-W, Tau, S.-I. and Chuang, L.-W, J. Am. Chem. Soc,1993, 115,5941.
McDaniel, K.F, Kracker, L.R. II and Thamburaj, P.K, Tetrahedron Lett., 1990, 31, 2373.
Roell, B.C. Jr, McDaniel, K.F, Vaughan, W.S. and Macy, T.S, Organometallics, 1993, 12, 224.
Kündig, E.P. and Simmons, D.P, J. Chem. Soc, Chem. Commun., 1983, 1320.
Kündig, E.P, Inage, M. and Bernardinelli, G, Organometallics, 1991, 10, 2921.
Kündig, E.P, Bernardinelli, G, Liu, R. and Ripa, A, J. Am. Chem. Soc., 1991, 113, 9676; (b) Kündig, E.P, Ripa, A, Liu, R. and Bernardinelli, G, J. Org. Chem., 1994, 59, 4773.
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1996 Springer Science+Business Media Dordrecht
About this chapter
Cite this chapter
Stephenson, G.R. (1996). Stoichiometric π-complexes in asymmetric synthesis. In: Stephenson, G.R. (eds) Advanced Asymmetric Synthesis. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-0797-9_16
Download citation
DOI: https://doi.org/10.1007/978-94-007-0797-9_16
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-010-3731-0
Online ISBN: 978-94-007-0797-9
eBook Packages: Springer Book Archive