Highly enantioselective catalytic conjugate addition of N-heterocycles to α,β-unsaturated ketones and imides

Angewandte Chemie - International Edition

Volumn 44, Issue 16, 2005, Pages 2393-2397

  Gandelman, Mark ^a   Jacobsen, Eric N ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

Aluminum; Asymmetric catalysis; Heterocycles; Nucleobases; Synthetic methods

Indexed keywords

ADDITION REACTIONS; ALUMINUM; AMINES; CATALYSIS; COMPLEXATION;

CONJUGATE ADDITION; ENONES; IMIDES; NUCLEOPHILES;

KETONES;

HETEROCYCLIC COMPOUND; IMIDE; KETONE;

ARTICLE; CATALYSIS; CHEMISTRY; STEREOISOMERISM; X RAY CRYSTALLOGRAPHY;

CATALYSIS; CRYSTALLOGRAPHY, X-RAY; HETEROCYCLIC COMPOUNDS; IMIDES; KETONES; STEREOISOMERISM;

EID: 18044395960     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200463058     Document Type: Article

References (40)

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3. For discussions on the importance of chiral N-heterocycles, see: a) A. F. Pozharskii, A. T. Soldatenkov, A. R. Katritzky, Heterocycles in Life and Society, Wiley, New York, 1997; b) M. Shipman, Contemp. Org. Synth. 1995, 2, 1.
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6. Conjugate additions of indoles at C3 have been developed: a) J. F. Austin, D. W. C. MacMillan, J. Am. Chem. Soc. 2002, 124, 1172; the only reported conjugate additions of nitrogen-centered nucleophiles have afforded racemic products, usually as mixtures of regioisomers: b) S. Guillarme, S. Legoupy, A.-M. Aubertin, C. Olicard, N. Bourgougnon, F. Huet, Tetrahedron 2003, 59, 2177; c) A. Esposito, M. G. Perino, M. Taddei, Eur. J. Org. Chem. 1999, 931; d) G. R. Geen, P. M. Kincey, Tetrahedron Lett. 1992, 33, 4609; e) E.-S. M. A. Yakoul, E. B. Pedersen, Chem. Scr. 1989, 29, 185; f) E. P. Lira, C. W. Hoffman, J. Org. Chem. 1966, 31, 2188; g) R. H. Wiley, N. R. Smith, D. M. Johnson, J. Moffat, J. Am. Chem. Soc. 1954, 76, 4933.
7. Conjugate additions of indoles at C3 have been developed: a) J. F. Austin, D. W. C. MacMillan, J. Am. Chem. Soc. 2002, 124, 1172; the only reported conjugate additions of nitrogen-centered nucleophiles have afforded racemic products, usually as mixtures of regioisomers: b) S. Guillarme, S. Legoupy, A.-M. Aubertin, C. Olicard, N. Bourgougnon, F. Huet, Tetrahedron 2003, 59, 2177; c) A. Esposito, M. G. Perino, M. Taddei, Eur. J. Org. Chem. 1999, 931; d) G. R. Geen, P. M. Kincey, Tetrahedron Lett. 1992, 33, 4609; e) E.-S. M. A. Yakoul, E. B. Pedersen, Chem. Scr. 1989, 29, 185; f) E. P. Lira, C. W. Hoffman, J. Org. Chem. 1966, 31, 2188; g) R. H. Wiley, N. R. Smith, D. M. Johnson, J. Moffat, J. Am. Chem. Soc. 1954, 76, 4933.
8. Conjugate additions of indoles at C3 have been developed: a) J. F. Austin, D. W. C. MacMillan, J. Am. Chem. Soc. 2002, 124, 1172; the only reported conjugate additions of nitrogen-centered nucleophiles have afforded racemic products, usually as mixtures of regioisomers: b) S. Guillarme, S. Legoupy, A.-M. Aubertin, C. Olicard, N. Bourgougnon, F. Huet, Tetrahedron 2003, 59, 2177; c) A. Esposito, M. G. Perino, M. Taddei, Eur. J. Org. Chem. 1999, 931; d) G. R. Geen, P. M. Kincey, Tetrahedron Lett. 1992, 33, 4609; e) E.-S. M. A. Yakoul, E. B. Pedersen, Chem. Scr. 1989, 29, 185; f) E. P. Lira, C. W. Hoffman, J. Org. Chem. 1966, 31, 2188; g) R. H. Wiley, N. R. Smith, D. M. Johnson, J. Moffat, J. Am. Chem. Soc. 1954, 76, 4933.
9. Conjugate additions of indoles at C3 have been developed: a) J. F. Austin, D. W. C. MacMillan, J. Am. Chem. Soc. 2002, 124, 1172; the only reported conjugate additions of nitrogen-centered nucleophiles have afforded racemic products, usually as mixtures of regioisomers: b) S. Guillarme, S. Legoupy, A.-M. Aubertin, C. Olicard, N. Bourgougnon, F. Huet, Tetrahedron 2003, 59, 2177; c) A. Esposito, M. G. Perino, M. Taddei, Eur. J. Org. Chem. 1999, 931; d) G. R. Geen, P. M. Kincey, Tetrahedron Lett. 1992, 33, 4609; e) E.-S. M. A. Yakoul, E. B. Pedersen, Chem. Scr. 1989, 29, 185; f) E. P. Lira, C. W. Hoffman, J. Org. Chem. 1966, 31, 2188; g) R. H. Wiley, N. R. Smith, D. M. Johnson, J. Moffat, J. Am. Chem. Soc. 1954, 76, 4933.
10. Conjugate additions of indoles at C3 have been developed: a) J. F. Austin, D. W. C. MacMillan, J. Am. Chem. Soc. 2002, 124, 1172; the only reported conjugate additions of nitrogen-centered nucleophiles have afforded racemic products, usually as mixtures of regioisomers: b) S. Guillarme, S. Legoupy, A.-M. Aubertin, C. Olicard, N. Bourgougnon, F. Huet, Tetrahedron 2003, 59, 2177; c) A. Esposito, M. G. Perino, M. Taddei, Eur. J. Org. Chem. 1999, 931; d) G. R. Geen, P. M. Kincey, Tetrahedron Lett. 1992, 33, 4609; e) E.-S. M. A. Yakoul, E. B. Pedersen, Chem. Scr. 1989, 29, 185; f) E. P. Lira, C. W. Hoffman, J. Org. Chem. 1966, 31, 2188; g) R. H. Wiley, N. R. Smith, D. M. Johnson, J. Moffat, J. Am. Chem. Soc. 1954, 76, 4933.
11. Conjugate additions of indoles at C3 have been developed: a) J. F. Austin, D. W. C. MacMillan, J. Am. Chem. Soc. 2002, 124, 1172; the only reported conjugate additions of nitrogen-centered nucleophiles have afforded racemic products, usually as mixtures of regioisomers: b) S. Guillarme, S. Legoupy, A.-M. Aubertin, C. Olicard, N. Bourgougnon, F. Huet, Tetrahedron 2003, 59, 2177; c) A. Esposito, M. G. Perino, M. Taddei, Eur. J. Org. Chem. 1999, 931; d) G. R. Geen, P. M. Kincey, Tetrahedron Lett. 1992, 33, 4609; e) E.-S. M. A. Yakoul, E. B. Pedersen, Chem. Scr. 1989, 29, 185; f) E. P. Lira, C. W. Hoffman, J. Org. Chem. 1966, 31, 2188; g) R. H. Wiley, N. R. Smith, D. M. Johnson, J. Moffat, J. Am. Chem. Soc. 1954, 76, 4933.
12. Conjugate additions of indoles at C3 have been developed: a) J. F. Austin, D. W. C. MacMillan, J. Am. Chem. Soc. 2002, 124, 1172; the only reported conjugate additions of nitrogen-centered nucleophiles have afforded racemic products, usually as mixtures of regioisomers: b) S. Guillarme, S. Legoupy, A.-M. Aubertin, C. Olicard, N. Bourgougnon, F. Huet, Tetrahedron 2003, 59, 2177; c) A. Esposito, M. G. Perino, M. Taddei, Eur. J. Org. Chem. 1999, 931; d) G. R. Geen, P. M. Kincey, Tetrahedron Lett. 1992, 33, 4609; e) E.-S. M. A. Yakoul, E. B. Pedersen, Chem. Scr. 1989, 29, 185; f) E. P. Lira, C. W. Hoffman, J. Org. Chem. 1966, 31, 2188; g) R. H. Wiley, N. R. Smith, D. M. Johnson, J. Moffat, J. Am. Chem. Soc. 1954, 76, 4933.
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15. For applications as promising anticancer and antiviral chemotherapeutic agents, see: a) R. T. Walker, M. J. Gait in Nucleic Acids in Chemistry and Biochemistry (Eds.: G. M. Blackburn, M. J. Gait), IRL, Oxford, 1990, chap. 4, and references therein: b) L. A. Agrofoglio, S. R. Challand, Acyclic, Carbocyclic and L-Nucleosides, Kluwer Academic, Dordrecht, 1998; c) E. De Clercq, J. Med. Chem. 1995, 38, 2491.
16. For applications as promising anticancer and antiviral chemotherapeutic agents, see: a) R. T. Walker, M. J. Gait in Nucleic Acids in Chemistry and Biochemistry (Eds.: G. M. Blackburn, M. J. Gait), IRL, Oxford, 1990, chap. 4, and references therein: b) L. A. Agrofoglio, S. R. Challand, Acyclic, Carbocyclic and L-Nucleosides, Kluwer Academic, Dordrecht, 1998; c) E. De Clercq, J. Med. Chem. 1995, 38, 2491.
17. For applications as promising anticancer and antiviral chemotherapeutic agents, see: a) R. T. Walker, M. J. Gait in Nucleic Acids in Chemistry and Biochemistry (Eds.: G. M. Blackburn, M. J. Gait), IRL, Oxford, 1990, chap. 4, and references therein: b) L. A. Agrofoglio, S. R. Challand, Acyclic, Carbocyclic and L-Nucleosides, Kluwer Academic, Dordrecht, 1998; c) E. De Clercq, J. Med. Chem. 1995, 38, 2491.
18. a) J. K. Myers, E. N. Jacobsen, J. Am. Chem. Soc. 1999. 121, 8959;
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22. e) addition of nitrile derivatives and hydrazoic acid to α,β-unsaturatcd ketones: M. S. Taylor, D. Zalatan, A. M. Lerchner, E. N. Jacobsen, J. Am. Chem. Soc. 2005, 127, 1313;
23. see also: f) S. C. Jha, N. N. Joshi, Tetrahedron: Asymmetry 2001, 12, 2463.
24. For detailed reviews of the properties, reactivity, and applications of studied heterocycles, see: a) purines: G. Shaw, H. Wamhoff, R. N. Butler in Comprehensive Heterocyclic Chemistry, Vol.5 (Eds.: A. L. Katritzky, C. W. Rees, K. T. Potts). Pergamon, Oxford, 1984, chap. 4.09; b) benzotriazole and 1,2,3-triazole: G. Shaw, H. Wamhoff, R. N. Butler in Comprehensive Heterocyclic Chemistry, Vol. 5 (Eds.: A. L. Katritzky, C. W. Rees, K. T. Potts), Pergamon, Oxford, 1984, chap. 4.11; c) tetrazole: G. Shaw, H. Wamhoff, R. N. Butler in Comprehensive Heterocyclic Chemistry, Vol. 5 (Eds.: A. L. Katritzky, C. W. Rees, K. T. Potts), Pergamon, Oxford, 1984, chap. 4.13.
25. For detailed reviews of the properties, reactivity, and applications of studied heterocycles, see: a) purines: G. Shaw, H. Wamhoff, R. N. Butler in Comprehensive Heterocyclic Chemistry, Vol.5 (Eds.: A. L. Katritzky, C. W. Rees, K. T. Potts). Pergamon, Oxford, 1984, chap. 4.09; b) benzotriazole and 1,2,3-triazole: G. Shaw, H. Wamhoff, R. N. Butler in Comprehensive Heterocyclic Chemistry, Vol. 5 (Eds.: A. L. Katritzky, C. W. Rees, K. T. Potts), Pergamon, Oxford, 1984, chap. 4.11; c) tetrazole: G. Shaw, H. Wamhoff, R. N. Butler in Comprehensive Heterocyclic Chemistry, Vol. 5 (Eds.: A. L. Katritzky, C. W. Rees, K. T. Potts), Pergamon, Oxford, 1984, chap. 4.13.
26. For detailed reviews of the properties, reactivity, and applications of studied heterocycles, see: a) purines: G. Shaw, H. Wamhoff, R. N. Butler in Comprehensive Heterocyclic Chemistry, Vol.5 (Eds.: A. L. Katritzky, C. W. Rees, K. T. Potts). Pergamon, Oxford, 1984, chap. 4.09; b) benzotriazole and 1,2,3-triazole: G. Shaw, H. Wamhoff, R. N. Butler in Comprehensive Heterocyclic Chemistry, Vol. 5 (Eds.: A. L. Katritzky, C. W. Rees, K. T. Potts), Pergamon, Oxford, 1984, chap. 4.11; c) tetrazole: G. Shaw, H. Wamhoff, R. N. Butler in Comprehensive Heterocyclic Chemistry, Vol. 5 (Eds.: A. L. Katritzky, C. W. Rees, K. T. Potts), Pergamon, Oxford, 1984, chap. 4.13.
27. Enones that bear aromatic β-substituents exhibited low reactivity, even under forcing conditions. Cyclic enones such as 2-cyclopentenone and 2-cyclohexenone underwent conjugate addition with only moderate enantioselectivity (30% ee with 2-cyclohexenone under the conditions outlined in Table 1).
28. Prepared according to the literature procedure: S. Dey, P. Garner, J. Org. Chem. 2000, 65, 7697.
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31. N-Boc-protected adenine exhibited poor reactivity with α,β-unsaturated imides even at elevated temperatures.
32. CCD0-259667 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
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39. III complexes hearing polyligating hetecrocyclic compounds are known: a) C. M. Mikulski, R. De Prince, G. W. Madison, M. Gaul, N. M. Karayannis, Inorg. Chim. Acta 1987, 138, 55; b) C. M. Mikulski, S. Cocco, L. Mattucci, N. Defranco, L. Weiss, N. M. Karayannis, Inorg. Chim. Acta 1982, 67, 173.
40. III complexes hearing polyligating hetecrocyclic compounds are known: a) C. M. Mikulski, R. De Prince, G. W. Madison, M. Gaul, N. M. Karayannis, Inorg. Chim. Acta 1987, 138, 55; b) C. M. Mikulski, S. Cocco, L. Mattucci, N. Defranco, L. Weiss, N. M. Karayannis, Inorg. Chim. Acta 1982, 67, 173.