Abstract
The development of catalytic asymmetric reactions is one of the major areas of research in the field of organic chemistry. So far, a number of chiral catalysts have been reported, and some of them have exhibited a much higher catalytic efficiency than enzymes, which are natural catalysts (Herrmann and Cornils 1996; Noyori 1994; Ojima 1994; Bosnich 1986; Morrison 1985). Most of the synthetic asymmetric catalysts, however, show limited activity in terms of either enantioselectivity or chemical yields. The major difference between synthetic asymmetric catalysts and enzymes is that the former activate only one side of the substrate in an intermolecular reaction, whereas the latter not only activate both sides of the substrate but can also control the orientation of the substrate. If this kind of synergistic cooperation can be realized in synthetic asymmetric catalysis, the concept will open up a new field in asymmetric synthesis, and a wide range of applications may well ensue. This minireview covers two types of asymmetric two-center catalyses promoted by complexes showing Lewis acidity and Br0nsted basicity and/or Lewis acidity and Lewis basicity (Steinhagen and Helmchen 1996; Shibasaki et al. 1997).
Keywords
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
This is a preview of subscription content, log in via an institution.
Buying options
Tax calculation will be finalised at checkout
Purchases are for personal use only
Learn about institutional subscriptionsPreview
Unable to display preview. Download preview PDF.
References
Arai T, Bougaini M, Sasai If, Shibasaki M (1996a) Catalytic asymmetric synthesis of oc-hydroxy phosphonates using the Al-Li-BINOL complex. J Org Chem 61:2926–2927
Arai T, Sasai H, Aoe K, Okamura K, Date T, Shibasaki M (1996b) A new multifunctional heterobimetallic asymmetric catalyst for Michael additions and tandem Michael-aldol reactions. Angew Chem Int Ed Engl 35:104–106
Arai T, Yamada YMA, Yamamoto N, Sasai H, Shibasaki M (1996c) Self-assembly of heterobimetallic complexes and reactive nucleophiles: a general strategy for the activation of asymmetric reactions promoted by heterobimetallic catalysis. Chem Eur J 2:1368–1372
Bosnich B (1986) Asymmetric catalysis. Nijhoff, Dordrecht
Bougauchi M, Watanabe S, Arai T, Sasai H, Shibasaki M (1997) Catalytic asymmetric epoxidation of oc,ß-unsaturated ketones promoted by lanthanoid complexes. J Am Chem Soc 119:2329–2330
Corey EJ, Bakshi RK, Shibata S (1987) Highly enantioselective borane reduction of ketones catalyzed by chiral oxazaborolidines. Mechanism and synthetic implications. J Am Chem Soc 109:5551–5553
Daikai K, Kamaura M, Inanaga J (1998) Remarkable ligand effect on the enan-tioselectivity of the chiral lanthanum complex-catalyzed asymmetric epoxidation of enones. Tetrahedron Lett 39:7321–7322
Denmark SE, Wong K-T, Stavenger RA (1997) Highly selective asymmetric aldol additions of ketone enolates. J Am Chem Soc 119:2333–2334
Emori E, Arai T, Sasai H, Shibasaki M (1998) A catalytic Michael addition of thiols to oc,ß-unsaturated carbonyl compounds: asymmetric protonations. J Am Chem Soc 120:4043–4044
Evans DA, Burgey CS, Paras NA, Vojkovsky T, Tregay SW (1998) C2-sym-metric copper(II) complexes as chiral Lewis acids. Enantioselective catalysis of the glyoxylate-ene reaction. J Am Chem Soc 120:5824–5825
Fessner W-D, Schneider A, Held H, Sinerius G, Walter C, Hixon M, Schloss JV (1996) The mechanism of class II, metal-dependent aldolases. Angew Chem Int Ed Engl 35:2219–2221
Funabashi K, Saida Y, Kanai M, Arai T. Sasai, H, Shibasaki M (1998) Catalytic asymmetric Michael addition of nitromethane to enones controlled by (R)-LPB. Tetrahedron Lett 39: 7557–7558
Gröger H, Saida Y, Arai S, Martens J, Sasai H, Shibasaki M (1996) First catalytic asymmetric hydrophosphonylation of cyclic imines: highly efficient enantioselective approach to a 4-thiazolidinylphosphonate via chiral titanium and lanthanoid catalysis. Tetrahedron Lett 37:9291–9292
Gröger H, Saida Y, Sasai H, Yamaguchi K, Martens J, Shibasaki M (1998) A new and highly efficient asymmetric route to cyclic oc-amino phosphonates: the first catalytic enantioselective hydrophosphonylation of cyclic imines catalyzed by chiral heterobimetallic lanthanoid complexes J Am Chem Soc 120:3089–3103
Hamashima Y, Sawada D, Kanai M, Shibasaki M (1999) A new bifunctional asymmetric catalysis: an efficient catalytic asymmetric cyanosilylation of aldehydes. J Am Chem Soc 121:2641–2642
Herrmann WA, Cornils B (1996) Applied homogeneous catalysis with or-ganometallic compounds. VCH, Weinheim
Hwang C-D, Hwang D-R, Uang B-J (1998) Enantioselective addition of trimethylsilyl cyanide to aldehydes induced by a new chiral Ti (IV) complex. J Org Chem 63:6762–6763
Iida T, Yamamoto N, Sasai H, Shibasaki M (1997) New asymmetric reactions using a gallium complex: a highly enantioselective ring opening of epoxides with thiols catalyzed by a gallium-lithium-bis(binaphthoxide) complex. J Am Chem Soc 119:4783–4784
Iida T, Yamamoto N, Woo H-G, Shibasaki M (1998) Enantioselective ring opening of epoxides with 4-methoxyphenol catalyzed by gallium heterobimetallic complexes: an efficient method for the synthesis of optically active 1,2-diol monoethers. Angew Chem Int Ed Engl 37:2223–2226
Kobayashi S, Tsuchiya Y, Mukaiyama T (1991) Enantioselective addition reaction of trimethylsilyl cyanide with aldehydes using a chiral tin (II) Lewis acid. Chem Lett: 38 541–544
Krüger J, Carreira EM (1998) Apparent catalytic generation of chiral metal enolates; enantioselective dienolate additions to aldehydes mediated by Tol-BINAP Cu(II) fluoride complexes. J Am Chem Soc 120:837–838
Morrison JD (1985) Asymmetric synthesis, vol 5. Academic, Orlando
Nara S, Toshima H, Ichihara A (1997) Asymmetric total syntheses of (+)-coro-nafacic acid and (+)-coronatine, Phytotoxins isolated from Pseudomonas syringae pathovars. Tetrahedron 53:9509–9524
Noyori R (1994) Asymmetric catalysis in organic synthesis. Wiley, New York
Noyori R, Kitamura M (1991) Enantioselective addition of organometallic reagents to carbonyl compounds: chirality transfer, multiplication, and amplification. Angew Chem Int Ed Engl 30:49–69
Ojima I (1994) Catalytic asymmetric synthesis. VCH, New York
Sasai H, Suzuki T, Arai S, Arai T, Shibasaki M (1992) Basic character of rare earth metal alkoxides. Utilization in catalytic C-C bond-forming reactions and catalytic asymmetric nitroaldol reactions. J Am Chem Soc 114:4418–4420
Sasai H, Suzuki T, Itoh N, Shibasaki M (1993a) Catalytic nitroaldol reactions. A new practical method for the preparation of the optically active lanthanum complex. Tetrahedron Lett 34:851–854
Sasai H, Suzuki T, Itoh N, Arai S, Shibasaki M (1993b) Effect of rare earth metals on the catalytic asymmetric nitroaldol reaction. Tetrahedron Lett 34:2657–2660
Sasai H, Itoh N, Suzuki T, Shibasaki M (1993c) Catalytic asymmetric nitroaldol reaction: an efficient synthesis of (S) propranolol using the lanthanum binaphthol complex. Tetrahedron Lett 34:855–858
Sasai H, Suzuki T, Itoh N, Tanaka K, Date T, Okamura K, Shibasaki M (1993d) Catalytic asymmetric nitroaldol reaction using optically active rare earth BINOL complexes: investigation of the catalyst structure. J Am Chem Soc 115:10372–10373
Sasai H, Yamada YMA, Suzuki T, Shibasaki M (1994a) Synthesis of (S)-13 pindolol and [3’- C]-(R)-(-)-pindoloI utilizing a lanthanum-lithium-(R)-BINOL ((R)-LLB) catalyzed nitroaldol reaction. Tetrahedron 50:12313–12318
Sasai H, Kim W-S, Suzuki T, Shibasaki M, Mitsuda M, Hasegawa J, Ohashi J (1994b) Diastereoselective catalytic asymmetric nitroaldol reaction utilizing rare earth-Li-(R)-BINOL complex. A highly efficient synthesis of norstatin. Tetrahedron Lett 35:6123–6126
Sasai H, Arai T, Satow Y, Houk KN, Shibasaki M (1995a) The first heterobi-metallic multifunctional asymmetric catalyst. J Am Chem Soc 117:6194–6198
Sasai H, Suzuki T, Itoh N, Shibasaki M (1995b) Catalytic asymmetric synthesis of propranolol and metoprolol using La-Li-BINOL complex. Appl Or-ganomet Chem 9:421–426
Sasai H, Tokunaga T, Watanabe S, Suzuki T, Itoh N, Shibasaki M, (1995c) Efficient diastereoselective and enantioselective nitroaldol reactions from pro-chiral starting materials. Utilization of La-Li-6,6’-disubstituted BINOL complexes as asymmetric catalysts. J Org Chem 60:7388–7389
Sasai H, Arai S, Tahara Y, Shibasaki M (1995d) Catalytic asymmetric synthesis of oc-aniino phosphonates using lanthanoid-potassium-BINOL complexes. J Org Chem 60:6656–6657
Sasai H, Emori E, Arai T, Shibasaki M (1996) Catalytic asymmetric Michael reactions promoted by the La-Na-BINOL complex (LSB). Enantioface selection on Michael donors. Tetrahedron Lett 37:5561–5564
Sasai H, Bougauchi B, Arai T, Shibaski M (1997a) Enantioselective synthesis of oc-hydroxy phosphonates using the La-Li3-tris(binaphthoxide) catalyst (LLB), prepared by an improved method. Tetrahedron Lett 38:2717–2720
Sasai H, Watanabe S, Shibasaki M (1997b) A new practical preparation method for lanthanum-lithium-binaphthol catalysts (LLBs) for use in asymmetric nitroaldol reactions. Enantiomer 2:267–271
Shibasaki M, Sasai H, Arai T (1997) Asymmetric catalysis with heterobimetal-lic compounds. Angew Chem Int Ed Engl 36:1236–1256
Shimizu S, Ohori K, Arai T, Sasai H, Shibasaki M (1998) A catalytic asymmetric synthesis of tubifolidine. J Org Chem 63:7547–7551
Steinhagen H, Helmchen G (1996) Asymmetric two-center catalysis: learning from nature. Angew Chem Int Ed Engl 35:2339–2342
Takaoka E, Yoshikawa N, Yamada YMA, Sasai H, Shibasaki M (1997) Catalytic asymmetric synthesis of arbutamine. Heterocycles 46:157–163
Tokunaga M. Larrow, JF, Kakiuchi F, Jacobsen EN (1997) Asymmetric catalysis with water: efficient kinetic resolution of terminal epoxides by means of catalytic hydrolysis. Science 277:936–938
Watanabe S, Arai T, Sasai H, Bougauchi M, Shibasaki M (1998a) The first catalytic enantioselective synthesis of ds-epoxyketones from ds-enones. J Org Chem 63:8090–8091
Watanabe S, Kobayashi Y, Arai T, Sasai H, Bougauchi M, Shibasaki M (1998b) Water vs. desiccant. Improvement of Yb-BINOL complex-catalyzed enantioselective epoxidation of enones. Tetrahedron Lett 39:7353–7356
Yamada K, Arai T, Sasai H, Shibasaki M (1998) A catalytic asymmetric synthesis of 11-deoxy-PGFla using ALB, a heterobimetallic multifunctional asymmetric complex. J Org Chem 63:3666–3672
Yamada YMA, Yoshikawa N, Sasai H, Shibasaki M (1997) Direct catalytic asymmetric aldol reactions of aldehydes and unmodified ketones. Angew Chem Int Ed Engl 36:1871–1873
Yamakoshi K, Harwood S, Kanai M, Shibasaki M (1999) Catalytic asymmetric addition of diphenylphosphine oxide to cyclic imines. Tetrahedron Lett 40:2565–2568
Yamasaki S, Iida T, Shibasaki M (1999) Direct catalytic asymmetric Mannich-type reaction of unmodified ketones utilizing the coopoeration of an AlLi-bis(binaphthoxide) complex and La(OTf)3 H2O. Tetrahedron Lett 40:307–310
Yanagisawa A, Matsumoto Y, Nakashima H, Asakawa K, Yamamoto H (1997) Enantioselective aldol reaction of tin enolates with aldehydes catalyzed by BINAP silver(I) complex. Am Chem Soc 119:9319–9320
Yoshikawa N, Yamada YMA, Das J, Sasai H, Shibasaki M (2000) Direct catalytic asymmetric aldol reaction. J Am Chem Soc 121:4168–4177
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2000 Springer-Verlag Berlin Heidelberg
About this paper
Cite this paper
Shibasaki, M. (2000). Multifunctional Asymmetric Catalysis. In: Mulzer, J., Bohlmann, R. (eds) The Role of Natural Products in Drug Discovery. Ernst Schering Research Foundation Workshop, vol 32. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-04042-3_11
Download citation
DOI: https://doi.org/10.1007/978-3-662-04042-3_11
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-662-04044-7
Online ISBN: 978-3-662-04042-3
eBook Packages: Springer Book Archive