Multifunctional Asymmetric Catalysis

  • M. Shibasaki
Conference paper
Part of the Ernst Schering Research Foundation Workshop book series (SCHERING FOUND, volume 32)


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).


Phosphine Oxide Aldol Reaction Heterobimetallic Complex Aldol Product Trimethylsilyl Cyanide 
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.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 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 61:2926–2927PubMedCrossRefGoogle Scholar
  2. 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 35:104–106CrossRefGoogle Scholar
  3. 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 2:1368–1372CrossRefGoogle Scholar
  4. Bosnich B (1986) Asymmetric catalysis. Nijhoff, DordrechtGoogle Scholar
  5. 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 119:2329–2330CrossRefGoogle Scholar
  6. 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 109:5551–5553CrossRefGoogle Scholar
  7. 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 39:7321–7322CrossRefGoogle Scholar
  8. Denmark SE, Wong K-T, Stavenger RA (1997) Highly selective asymmetric aldol additions of ketone enolates. J Am Chem Soc 119:2333–2334CrossRefGoogle Scholar
  9. 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 120:4043–4044CrossRefGoogle Scholar
  10. 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 120:5824–5825CrossRefGoogle Scholar
  11. 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 35:2219–2221CrossRefGoogle Scholar
  12. 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: 7557–7558CrossRefGoogle Scholar
  13. 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 37:9291–9292CrossRefGoogle Scholar
  14. 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 120:3089–3103CrossRefGoogle Scholar
  15. 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 121:2641–2642CrossRefGoogle Scholar
  16. Herrmann WA, Cornils B (1996) Applied homogeneous catalysis with or-ganometallic compounds. VCH, WeinheimGoogle Scholar
  17. 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 63:6762–6763PubMedCrossRefGoogle Scholar
  18. 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 119:4783–4784CrossRefGoogle Scholar
  19. 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 37:2223–2226CrossRefGoogle Scholar
  20. Kobayashi S, Tsuchiya Y, Mukaiyama T (1991) Enantioselective addition reaction of trimethylsilyl cyanide with aldehydes using a chiral tin (II) Lewis acid. Chem Lett: 38 541–544CrossRefGoogle Scholar
  21. 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 120:837–838CrossRefGoogle Scholar
  22. Morrison JD (1985) Asymmetric synthesis, vol 5. Academic, OrlandoGoogle Scholar
  23. Nara S, Toshima H, Ichihara A (1997) Asymmetric total syntheses of (+)-coro-nafacic acid and (+)-coronatine, Phytotoxins isolated from Pseudomonas syringae pathovars. Tetrahedron 53:9509–9524CrossRefGoogle Scholar
  24. Noyori R (1994) Asymmetric catalysis in organic synthesis. Wiley, New YorkGoogle Scholar
  25. Noyori R, Kitamura M (1991) Enantioselective addition of organometallic reagents to carbonyl compounds: chirality transfer, multiplication, and amplification. Angew Chem Int Ed Engl 30:49–69CrossRefGoogle Scholar
  26. Ojima I (1994) Catalytic asymmetric synthesis. VCH, New YorkGoogle Scholar
  27. 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 114:4418–4420CrossRefGoogle Scholar
  28. 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 34:851–854CrossRefGoogle Scholar
  29. Sasai H, Suzuki T, Itoh N, Arai S, Shibasaki M (1993b) Effect of rare earth metals on the catalytic asymmetric nitroaldol reaction. Tetrahedron Lett 34:2657–2660CrossRefGoogle Scholar
  30. 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 34:855–858CrossRefGoogle Scholar
  31. 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 115:10372–10373CrossRefGoogle Scholar
  32. 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 50:12313–12318CrossRefGoogle Scholar
  33. 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 35:6123–6126CrossRefGoogle Scholar
  34. Sasai H, Arai T, Satow Y, Houk KN, Shibasaki M (1995a) The first heterobi-metallic multifunctional asymmetric catalyst. J Am Chem Soc 117:6194–6198CrossRefGoogle Scholar
  35. 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 9:421–426CrossRefGoogle Scholar
  36. 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 60:7388–7389CrossRefGoogle Scholar
  37. Sasai H, Arai S, Tahara Y, Shibasaki M (1995d) Catalytic asymmetric synthesis of oc-aniino phosphonates using lanthanoid-potassium-BINOL complexes. J Org Chem 60:6656–6657CrossRefGoogle Scholar
  38. 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 37:5561–5564CrossRefGoogle Scholar
  39. 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 38:2717–2720CrossRefGoogle Scholar
  40. 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 2:267–271Google Scholar
  41. Shibasaki M, Sasai H, Arai T (1997) Asymmetric catalysis with heterobimetal-lic compounds. Angew Chem Int Ed Engl 36:1236–1256CrossRefGoogle Scholar
  42. Shimizu S, Ohori K, Arai T, Sasai H, Shibasaki M (1998) A catalytic asymmetric synthesis of tubifolidine. J Org Chem 63:7547–7551PubMedCrossRefGoogle Scholar
  43. Steinhagen H, Helmchen G (1996) Asymmetric two-center catalysis: learning from nature. Angew Chem Int Ed Engl 35:2339–2342CrossRefGoogle Scholar
  44. Takaoka E, Yoshikawa N, Yamada YMA, Sasai H, Shibasaki M (1997) Catalytic asymmetric synthesis of arbutamine. Heterocycles 46:157–163CrossRefGoogle Scholar
  45. 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 277:936–938PubMedCrossRefGoogle Scholar
  46. 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 63:8090–8091CrossRefGoogle Scholar
  47. 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 39:7353–7356CrossRefGoogle Scholar
  48. 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 63:3666–3672CrossRefGoogle Scholar
  49. Yamada YMA, Yoshikawa N, Sasai H, Shibasaki M (1997) Direct catalytic asymmetric aldol reactions of aldehydes and unmodified ketones. Angew Chem Int Ed Engl 36:1871–1873CrossRefGoogle Scholar
  50. Yamakoshi K, Harwood S, Kanai M, Shibasaki M (1999) Catalytic asymmetric addition of diphenylphosphine oxide to cyclic imines. Tetrahedron Lett 40:2565–2568CrossRefGoogle Scholar
  51. 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 40:307–310CrossRefGoogle Scholar
  52. 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 119:9319–9320CrossRefGoogle Scholar
  53. Yoshikawa N, Yamada YMA, Das J, Sasai H, Shibasaki M (2000) Direct catalytic asymmetric aldol reaction. J Am Chem Soc 121:4168–4177CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2000

Authors and Affiliations

  • M. Shibasaki

There are no affiliations available

Personalised recommendations