Catalytic asymmetric cyano-ethoxycarbonylation reaction of aldehydes using a YLi3tris(binaphthoxide) (YLB) complex: Mechanism and roles of achiral additives

Journal of the American Chemical Society

Volumn 127, Issue 10, 2005, Pages 3413-3422

  Yamagiwa, Noriyuki ^a   Tian, Jun ^a   Matsunaga, Shigeki ^a   Shibasaki, Masakatsu ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ACETONE; BIMETALS; CARBONYLATION; CATALYSTS; LITHIUM COMPOUNDS; OPTIMIZATION;

CYANOFORMATE; CYANOHYDRINS; PHOSPHINE OXIDE; REACTION PATHWAYS;

ALDEHYDES;

ALDEHYDE; CYANOHYDRIN; LITHIUM; NITRILE; PHOSPHINE DERIVATIVE; TRIS (2,6 DIMETHOXYPHENYL)PHOSPHINE OXIDE; UNCLASSIFIED DRUG;

ARTICLE; CARBONYLATION; CATALYSIS; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; CHIRALITY; CYANATION; ENANTIOSELECTIVITY; INFRARED RADIATION; REACTION ANALYSIS;

EID: 14944386585     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja042887v     Document Type: Article

References (49)

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3. For recent reviews on asymmetric cyanation reaction, see: (a) Brunel, J. M.; Holmes, I. P. Angew. Chem., Int. Ed. 2004, 43, 2752. (b) North, M. Tetrahedron: Asymmetry 2003, 14, 147. (c) Gröger, H. Chem.-Eur. J. 2001, 7, 5246. (d) Gregory, R. J. H. Chem. Rev. 1999, 99, 3949.
4. For recent reviews on asymmetric cyanation reaction, see: (a) Brunel, J. M.; Holmes, I. P. Angew. Chem., Int. Ed. 2004, 43, 2752. (b) North, M. Tetrahedron: Asymmetry 2003, 14, 147. (c) Gröger, H. Chem.-Eur. J. 2001, 7, 5246. (d) Gregory, R. J. H. Chem. Rev. 1999, 99, 3949.
5. Tian, S.-K.; Deng, L. J. Am. Chem. Soc. 2001, 123, 6195.
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10. During preparation of this manuscript, North and Belokon reported mechanistic studies concerning the structure of chiral Ti-salen catalyst in solution using various cyanide sources: Belokon, Y. N.; Blacker, A. J.; Carta, P.; Clutterbuck, L. A.; North, M. Tetrahedron 2004, 60, 10433.
11. (a) Tian, J.; Yamagiwa, N.; Matsunaga, S.; Shibasaki, M. Angew. Chem., Int. Ed. 2002, 41, 3636.
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13. With diethyl cyanophosphonate as a cyanide source: (c) Abiko, Y.; Yamagiwa, N.; Sugita, M.; Tian, J.; Matsunaga, S.; Shibasaki, M. Synlett 2004, 2434.
14. (a) Casas, J.; Baeza, A.; Sansano, J. M.; Nájera, C.; Saá, J. M. Tetrahedron: Asymmetry 2003, 14, 197.
15. 3SiCN: (c) Casas, J.; Nájera, C.; Sansano, J. M.; Saá, J. M. Org. Lett. 2002, 4, 2589.
16. 3SiCN: (c) Casas, J.; Nájera, C.; Sansano, J. M.; Saá, J. M. Org. Lett. 2002, 4, 2589.
17. For reviews of asymmetric catalysis using rare earth-alkali metal heterobimetallic complexes, see: (a) Shibasaki, M.; Yoshikawa, N. Chem. Rev. 2002, 102, 2187. (b) Shibasaki, M.; Sasai, H.; Arai, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 1236. For the preparation of YLB 1 complex and X-ray structure, see: (c) Aspinall, H. C.; Dwyer, J. L. M.; Greeves, N.; Steiner, A. Organometallics 1999, 18, 1366. (d) Aspinall, H. C.; Bickley, J. F. B.; Dwyer, L. M.; Greeves, N.; Kelly, R. V.; Steiner, A. Organometallics 2000, 19, 5416.
18. For reviews of asymmetric catalysis using rare earth-alkali metal heterobimetallic complexes, see: (a) Shibasaki, M.; Yoshikawa, N. Chem. Rev. 2002, 102, 2187. (b) Shibasaki, M.; Sasai, H.; Arai, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 1236. For the preparation of YLB 1 complex and X-ray structure, see: (c) Aspinall, H. C.; Dwyer, J. L. M.; Greeves, N.; Steiner, A. Organometallics 1999, 18, 1366. (d) Aspinall, H. C.; Bickley, J. F. B.; Dwyer, L. M.; Greeves, N.; Kelly, R. V.; Steiner, A. Organometallics 2000, 19, 5416.
19. For reviews of asymmetric catalysis using rare earth-alkali metal heterobimetallic complexes, see: (a) Shibasaki, M.; Yoshikawa, N. Chem. Rev. 2002, 102, 2187. (b) Shibasaki, M.; Sasai, H.; Arai, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 1236. For the preparation of YLB 1 complex and X-ray structure, see: (c) Aspinall, H. C.; Dwyer, J. L. M.; Greeves, N.; Steiner, A. Organometallics 1999, 18, 1366. (d) Aspinall, H. C.; Bickley, J. F. B.; Dwyer, L. M.; Greeves, N.; Kelly, R. V.; Steiner, A. Organometallics 2000, 19, 5416.
20. For reviews of asymmetric catalysis using rare earth-alkali metal heterobimetallic complexes, see: (a) Shibasaki, M.; Yoshikawa, N. Chem. Rev. 2002, 102, 2187. (b) Shibasaki, M.; Sasai, H.; Arai, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 1236. For the preparation of YLB 1 complex and X-ray structure, see: (c) Aspinall, H. C.; Dwyer, J. L. M.; Greeves, N.; Steiner, A. Organometallics 1999, 18, 1366. (d) Aspinall, H. C.; Bickley, J. F. B.; Dwyer, L. M.; Greeves, N.; Kelly, R. V.; Steiner, A. Organometallics 2000, 19, 5416.
21. (a) Yamagiwa, N.; Matsunaga, S.; Shibasaki, M. J. Am. Chem. Soc. 2003, 125, 16178.
22. For discussion of the reaction mechanism using anhydrous YLB as a catalyst, see: (b) Yamagiwa, N.; Matsunaga, S.; Shibasaki, M. Angew. Chem., Int. Ed. 2004, 43, 4493.
23. (a) Hamashima, Y.; Sawada, D.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 1999, 121, 2641.
24. For reviews, see also: (b) Shibasaki, M.; Kanai, M.; Funabashi, K. Chem. Commun. 2002, 1989. (c) Shibasaki, M.; Kanai, M. Chem. Pharm. Bull. 2001, 49, 511.
25. For reviews, see also: (b) Shibasaki, M.; Kanai, M.; Funabashi, K. Chem. Commun. 2002, 1989. (c) Shibasaki, M.; Kanai, M. Chem. Pharm. Bull. 2001, 49, 511.
26. For use of phosphine oxide to increase nucleophilicity of cyanide species generated from TMSCN in the catalytic asymmetric cyanosilylation reaction of aldehyde, see: Ryu, D. H.; Corey, E. J. J. Am. Chem. Soc. 2004, 126, 8106 and references therein.
27. Catalyst screening was performed without phosphine oxide and BuLi. Other rare earth-alkali metal heterobimetallic complexes gave less satisfactory results in terms of reaction rate and enantioselectivity. For example: Dy-Li-BINOL, 4 h, y. quant, 45% ee; Yb-Li-BINOL, 4 h, y. quant, 31% ee; Sc-Li-BINOL, 1 h, y. quant, 9% ee; Y-Na-BINOL, 0.5 h, y. quant, 0% ee; Y-K-BINOL, 5.5 h, y. quant, 8% ee.
28. 3P: 71% ee.
29. For the preparation of phosphine oxides, see: Kim, R. D.; Stevens, C. H. Polyhedron 1994, 13, 727. For the procedure, see Supporting Information.
30. 2O complex.
31. Although rare earth metal complexes with a coordination number higher than eight are well-known, maximum coordination number of rare earth metals in rare earth-alkali metal-BINOL (1:3:3) heterobimetallic complexes reported so far is seven, according to crystal structure analysis of various complexes. See refs 7, 16 and references therein. See, also: Aspinall, H. C. Chem. Rev, 2002, 102, 1807.
32. 2O with the Y metal center. For analysis of the heterobimetallic Yb complex, see: (a) Bari, L. D.; Lelli, M.; Pintacuda, G.; Pescitelli, G.; Marchetti, F.; Salvadori, P. J. Am. Chem, Soc. 2003, 125, 5549. (b) Bari, L. D.; Lelli, M.; Salvadori, P. Chem.-Eur. J. 2004, 10, 4594.
33. 2O with the Y metal center. For analysis of the heterobimetallic Yb complex, see: (a) Bari, L. D.; Lelli, M.; Pintacuda, G.; Pescitelli, G.; Marchetti, F.; Salvadori, P. J. Am. Chem, Soc. 2003, 125, 5549. (b) Bari, L. D.; Lelli, M.; Salvadori, P. Chem.-Eur. J. 2004, 10, 4594.
34. For examples of racemic reactions, see: (a) Scholl, M.; Lim, C.-K.; Fu, G. C. J. Org. Chem. 1995, 60, 6229 and references therein. (b) Okimoto, M.; Chiba, T. Synthesis 1996, 1188. (c) Berthiaume, D.; Poirier, D. Tetrahedron 2000, 56, 5995. For related racemic reaction using diethyl cyanophosphonate as a cyanide source, see: (d) Harusawa, S.; Yoneda, R.; Kurihara, T.; Hamada, Y.; Shioiri, T. Chem. Pharm. Bull. 1983, 31, 2932. (e) Kurihara, T.; Harusawa, S.; Yoneda, R. J. Synth. Org. Chem. Jpn. 1988, 46, 1164 and references therein.
35. For examples of racemic reactions, see: (a) Scholl, M.; Lim, C.-K.; Fu, G. C. J. Org. Chem. 1995, 60, 6229 and references therein. (b) Okimoto, M.; Chiba, T. Synthesis 1996, 1188. (c) Berthiaume, D.; Poirier, D. Tetrahedron 2000, 56, 5995. For related racemic reaction using diethyl cyanophosphonate as a cyanide source, see: (d) Harusawa, S.; Yoneda, R.; Kurihara, T.; Hamada, Y.; Shioiri, T. Chem. Pharm. Bull. 1983, 31, 2932. (e) Kurihara, T.; Harusawa, S.; Yoneda, R. J. Synth. Org. Chem. Jpn. 1988, 46, 1164 and references therein.
36. For examples of racemic reactions, see: (a) Scholl, M.; Lim, C.-K.; Fu, G. C. J. Org. Chem. 1995, 60, 6229 and references therein. (b) Okimoto, M.; Chiba, T. Synthesis 1996, 1188. (c) Berthiaume, D.; Poirier, D. Tetrahedron 2000, 56, 5995. For related racemic reaction using diethyl cyanophosphonate as a cyanide source, see: (d) Harusawa, S.; Yoneda, R.; Kurihara, T.; Hamada, Y.; Shioiri, T. Chem. Pharm. Bull. 1983, 31, 2932. (e) Kurihara, T.; Harusawa, S.; Yoneda, R. J. Synth. Org. Chem. Jpn. 1988, 46, 1164 and references therein.
37. For examples of racemic reactions, see: (a) Scholl, M.; Lim, C.-K.; Fu, G. C. J. Org. Chem. 1995, 60, 6229 and references therein. (b) Okimoto, M.; Chiba, T. Synthesis 1996, 1188. (c) Berthiaume, D.; Poirier, D. Tetrahedron 2000, 56, 5995. For related racemic reaction using diethyl cyanophosphonate as a cyanide source, see: (d) Harusawa, S.; Yoneda, R.; Kurihara, T.; Hamada, Y.; Shioiri, T. Chem. Pharm. Bull. 1983, 31, 2932. (e) Kurihara, T.; Harusawa, S.; Yoneda, R. J. Synth. Org. Chem. Jpn. 1988, 46, 1164 and references therein.
38. For examples of racemic reactions, see: (a) Scholl, M.; Lim, C.-K.; Fu, G. C. J. Org. Chem. 1995, 60, 6229 and references therein. (b) Okimoto, M.; Chiba, T. Synthesis 1996, 1188. (c) Berthiaume, D.; Poirier, D. Tetrahedron 2000, 56, 5995. For related racemic reaction using diethyl cyanophosphonate as a cyanide source, see: (d) Harusawa, S.; Yoneda, R.; Kurihara, T.; Hamada, Y.; Shioiri, T. Chem. Pharm. Bull. 1983, 31, 2932. (e) Kurihara, T.; Harusawa, S.; Yoneda, R. J. Synth. Org. Chem. Jpn. 1988, 46, 1164 and references therein.
39. Livinghouse, T. Org. Synth. 1984, 60, 126. Although LiH was used to generate LiCN from acetone cyanohydrin in the original report, we used LiHMDS instead of LiH to obtain LiCN with high purity. [Procedure: Caution! LiCN is highly toxic] To a stirred solution of acetone cyanohydrin in THF at 0°C was added 1 equiv of LiHMDS. The mixture was stirred at 0°C for 30 min, then solvent was evaporated under reduced pressure to afford colorless powder in quantitative yield. Because LiCN is highly hygroscopic, LiCN was handled under Ar and immediately used after preparation.
40. 2O (control experiment for Scheme 3), the results were 63% ee, 99% yield, after 2 h.
41. ConcIRT AF, version 3.5.0.4 software (METTLER TOLEDO Autochem), was used for mathematical treatment of IR spectra.
42. 2O would slowly attack 2 to generate LiCN (Table 1, entries 4-8).
43. In Figure 13, initial reaction rate is shown as relative rate. Rate with the lowest concentration of variable factor is defined as standard (relative rate = 1), and other rates are shown relative to the standard. In Figure 13a,c, kinetics were measured without adding acetone cyanohydrin 8. For detailed results of initial rate kinetics, see Supporting Information.
44. We assumed that Lewis basic phosphine oxide 3a would coordinate to the lithium cation and increase electron density of the cyanide anion, thus increasing nucleophilicity of the cyanide anion.
45. For ESI-MS spectra of YLB 1 under various conditions, see Supporting Information.
46. In the mechanistic studies of catalytic asymmetric reactions, the observed predominant species is not always an active species. For example, see: Landis, C.; Halpern, J. J. Am. Chem. Soc. 1987, 109, 1746.
47. 3:BuLi:BINOL = 0:2:1 mixture promoted the cyanation reaction of 4a smoothly, and 5a was obtained in 93% yield after 2 h at -78°C, but in only 2% ee. Thus, we speculate that dissociation of Y:Li:BINOL = 1:3:3 complex into Y:Li:BINOL = 1:1:2 complex and Y:Li:BINOL = 0:2:1 complex is less likely, and that Y:Li: BINOL = 1:3:3 would be the more probable framework of active species in the present reaction. Further quantitative analysis to unequivocally determine the structure of active species will be discussed elsewhere.
48. Because intensity of carbonyl absorbance of 4h was much weaker than that of 4a, the y-axis scale in Figure 15b is different from that in Figure 15a.
49. Kinetic dynamic resolution pathway was proposed by Deng et al. when using chiral Lewis base catalyst in asymmetric cyano-ethoxycarbonylation of ketones at -12 or -24°C. See ref 2.