Alkynylboronic esters as efficient dienophiles in cobalt-catalyzed Diels-Alder reactions

Angewandte Chemie - International Edition

Volumn 42, Issue 24, 2003, Pages 2795-2797

  Hilt, Gerhard ^a   Smolko, Konstantin I ^a  

^a PHILIPPS UNIVERSITY MARBURG   (Germany)

Author keywords

Alkynes; Boron compounds; Diels Alder reactions; Dihydroaromatic compounds; Suzuki reaction

Indexed keywords

CATALYSIS; COBALT; SYNTHESIS (CHEMICAL);

BUILDING BLOCKS;

ESTERS;

ALKADIENE; ALKYNYL GROUP; AROMATIC COMPOUND; BORONIC ACID DERIVATIVE; COBALT; ESTER DERIVATIVE; POLYCYCLIC AROMATIC COMPOUND; VINYL DERIVATIVE;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL REACTION; DIELS ALDER REACTION; OXIDATION; REACTION ANALYSIS; SYNTHESIS;

EID: 0038053109     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200351404     Document Type: Article

References (23)

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2. A. Suzuki, Pure Appl. Chem. 1994, 66, 213; A. Suzuki in Metal-Catalyzed Cross-Coupling Reactions (Eds.: F. Diederich, P. J. Stang), Wiley-VCH, Weinheim, 1998, chapt. 2, p. 49.
3. D. S. Matteson, J. O. Wasserbillig, J. Org. Chem. 1963, 28, 366; M. A. Silva, S. C. Pellegrinet, J. M. Goodman, J. Org. Chem. 2002, 67, 8203; D. A. Singleton, S.-W. Leung, J. Org. Chem. 1992, 57, 4796; S.-W. Leung, D. A. Singleton, J. Org. Chem. 1997, 62, 1955; D. A. Singleton, S.-H. Leing, J. Organomet. Chem. 1997, 544, 157; for an application in the Dötz reaction see: M. W. Davies, C. N. Johnson, J. P. A. Harrity, J. Org. Chem. 2001, 66, 3525; for an application in [3+2]-cycloadditions see: W. M. Davies, R. A. J. Wybrow, C. N. Johnson, J. P. A. Harrity, Chem. Commun. 2001, 1558; for the synthesis of the alkynylboron derivatives see: H. C. Brown, N. G. Bhat, M. Srebnik, Tetrahedron Lett. 1988, 29, 2631.
4. D. S. Matteson, J. O. Wasserbillig, J. Org. Chem. 1963, 28, 366; M. A. Silva, S. C. Pellegrinet, J. M. Goodman, J. Org. Chem. 2002, 67, 8203; D. A. Singleton, S.-W. Leung, J. Org. Chem. 1992, 57, 4796; S.-W. Leung, D. A. Singleton, J. Org. Chem. 1997, 62, 1955; D. A. Singleton, S.-H. Leing, J. Organomet. Chem. 1997, 544, 157; for an application in the Dötz reaction see: M. W. Davies, C. N. Johnson, J. P. A. Harrity, J. Org. Chem. 2001, 66, 3525; for an application in [3+2]-cycloadditions see: W. M. Davies, R. A. J. Wybrow, C. N. Johnson, J. P. A. Harrity, Chem. Commun. 2001, 1558; for the synthesis of the alkynylboron derivatives see: H. C. Brown, N. G. Bhat, M. Srebnik, Tetrahedron Lett. 1988, 29, 2631.
5. D. S. Matteson, J. O. Wasserbillig, J. Org. Chem. 1963, 28, 366; M. A. Silva, S. C. Pellegrinet, J. M. Goodman, J. Org. Chem. 2002, 67, 8203; D. A. Singleton, S.-W. Leung, J. Org. Chem. 1992, 57, 4796; S.-W. Leung, D. A. Singleton, J. Org. Chem. 1997, 62, 1955; D. A. Singleton, S.-H. Leing, J. Organomet. Chem. 1997, 544, 157; for an application in the Dötz reaction see: M. W. Davies, C. N. Johnson, J. P. A. Harrity, J. Org. Chem. 2001, 66, 3525; for an application in [3+2]-cycloadditions see: W. M. Davies, R. A. J. Wybrow, C. N. Johnson, J. P. A. Harrity, Chem. Commun. 2001, 1558; for the synthesis of the alkynylboron derivatives see: H. C. Brown, N. G. Bhat, M. Srebnik, Tetrahedron Lett. 1988, 29, 2631.
6. D. S. Matteson, J. O. Wasserbillig, J. Org. Chem. 1963, 28, 366; M. A. Silva, S. C. Pellegrinet, J. M. Goodman, J. Org. Chem. 2002, 67, 8203; D. A. Singleton, S.-W. Leung, J. Org. Chem. 1992, 57, 4796; S.-W. Leung, D. A. Singleton, J. Org. Chem. 1997, 62, 1955; D. A. Singleton, S.-H. Leing, J. Organomet. Chem. 1997, 544, 157; for an application in the Dötz reaction see: M. W. Davies, C. N. Johnson, J. P. A. Harrity, J. Org. Chem. 2001, 66, 3525; for an application in [3+2]-cycloadditions see: W. M. Davies, R. A. J. Wybrow, C. N. Johnson, J. P. A. Harrity, Chem. Commun. 2001, 1558; for the synthesis of the alkynylboron derivatives see: H. C. Brown, N. G. Bhat, M. Srebnik, Tetrahedron Lett. 1988, 29, 2631.
7. D. S. Matteson, J. O. Wasserbillig, J. Org. Chem. 1963, 28, 366; M. A. Silva, S. C. Pellegrinet, J. M. Goodman, J. Org. Chem. 2002, 67, 8203; D. A. Singleton, S.-W. Leung, J. Org. Chem. 1992, 57, 4796; S.-W. Leung, D. A. Singleton, J. Org. Chem. 1997, 62, 1955; D. A. Singleton, S.-H. Leing, J. Organomet. Chem. 1997, 544, 157; for an application in the Dötz reaction see: M. W. Davies, C. N. Johnson, J. P. A. Harrity, J. Org. Chem. 2001, 66, 3525; for an application in [3+2]-cycloadditions see: W. M. Davies, R. A. J. Wybrow, C. N. Johnson, J. P. A. Harrity, Chem. Commun. 2001, 1558; for the synthesis of the alkynylboron derivatives see: H. C. Brown, N. G. Bhat, M. Srebnik, Tetrahedron Lett. 1988, 29, 2631.
8. D. S. Matteson, J. O. Wasserbillig, J. Org. Chem. 1963, 28, 366; M. A. Silva, S. C. Pellegrinet, J. M. Goodman, J. Org. Chem. 2002, 67, 8203; D. A. Singleton, S.-W. Leung, J. Org. Chem. 1992, 57, 4796; S.-W. Leung, D. A. Singleton, J. Org. Chem. 1997, 62, 1955; D. A. Singleton, S.-H. Leing, J. Organomet. Chem. 1997, 544, 157; for an application in the Dötz reaction see: M. W. Davies, C. N. Johnson, J. P. A. Harrity, J. Org. Chem. 2001, 66, 3525; for an application in [3+2]-cycloadditions see: W. M. Davies, R. A. J. Wybrow, C. N. Johnson, J. P. A. Harrity, Chem. Commun. 2001, 1558; for the synthesis of the alkynylboron derivatives see: H. C. Brown, N. G. Bhat, M. Srebnik, Tetrahedron Lett. 1988, 29, 2631.
9. D. S. Matteson, J. O. Wasserbillig, J. Org. Chem. 1963, 28, 366; M. A. Silva, S. C. Pellegrinet, J. M. Goodman, J. Org. Chem. 2002, 67, 8203; D. A. Singleton, S.-W. Leung, J. Org. Chem. 1992, 57, 4796; S.-W. Leung, D. A. Singleton, J. Org. Chem. 1997, 62, 1955; D. A. Singleton, S.-H. Leing, J. Organomet. Chem. 1997, 544, 157; for an application in the Dötz reaction see: M. W. Davies, C. N. Johnson, J. P. A. Harrity, J. Org. Chem. 2001, 66, 3525; for an application in [3+2]-cycloadditions see: W. M. Davies, R. A. J. Wybrow, C. N. Johnson, J. P. A. Harrity, Chem. Commun. 2001, 1558; for the synthesis of the alkynylboron derivatives see: H. C. Brown, N. G. Bhat, M. Srebnik, Tetrahedron Lett. 1988, 29, 2631.
10. D. S. Matteson, J. O. Wasserbillig, J. Org. Chem. 1963, 28, 366; M. A. Silva, S. C. Pellegrinet, J. M. Goodman, J. Org. Chem. 2002, 67, 8203; D. A. Singleton, S.-W. Leung, J. Org. Chem. 1992, 57, 4796; S.-W. Leung, D. A. Singleton, J. Org. Chem. 1997, 62, 1955; D. A. Singleton, S.-H. Leing, J. Organomet. Chem. 1997, 544, 157; for an application in the Dötz reaction see: M. W. Davies, C. N. Johnson, J. P. A. Harrity, J. Org. Chem. 2001, 66, 3525; for an application in [3+2]-cycloadditions see: W. M. Davies, R. A. J. Wybrow, C. N. Johnson, J. P. A. Harrity, Chem. Commun. 2001, 1558; for the synthesis of the alkynylboron derivatives see: H. C. Brown, N. G. Bhat, M. Srebnik, Tetrahedron Lett. 1988, 29, 2631.
11. N. Guennouni, C. Rasset-Deloge, B. Carboni, M. Vaultier, Synlett 1992, 581; A. Kamabuchi, N. Miyaura, A. Suzuki, Tetrahedron Lett. 1993, 34, 4827; M. Shimizu, T. Kurahashi, T. Hiyama, Synlett 2001, 1006; J. Renoud, C.-D. Graf, L. Oberer. Angew. Chem. 2000, 112, 3231; Angew. Chem. Int. Ed. 2000, 39, 3101; F. Carreaux, F. Posseme, B. Carboni, A. Arrieta, B. Lecea, F. P. Cossio, J. Org. Chem. 2002, 67, 9153.
12. N. Guennouni, C. Rasset-Deloge, B. Carboni, M. Vaultier, Synlett 1992, 581; A. Kamabuchi, N. Miyaura, A. Suzuki, Tetrahedron Lett. 1993, 34, 4827; M. Shimizu, T. Kurahashi, T. Hiyama, Synlett 2001, 1006; J. Renoud, C.-D. Graf, L. Oberer. Angew. Chem. 2000, 112, 3231; Angew. Chem. Int. Ed. 2000, 39, 3101; F. Carreaux, F. Posseme, B. Carboni, A. Arrieta, B. Lecea, F. P. Cossio, J. Org. Chem. 2002, 67, 9153.
13. N. Guennouni, C. Rasset-Deloge, B. Carboni, M. Vaultier, Synlett 1992, 581; A. Kamabuchi, N. Miyaura, A. Suzuki, Tetrahedron Lett. 1993, 34, 4827; M. Shimizu, T. Kurahashi, T. Hiyama, Synlett 2001, 1006; J. Renoud, C.-D. Graf, L. Oberer. Angew. Chem. 2000, 112, 3231; Angew. Chem. Int. Ed. 2000, 39, 3101; F. Carreaux, F. Posseme, B. Carboni, A. Arrieta, B. Lecea, F. P. Cossio, J. Org. Chem. 2002, 67, 9153.
14. N. Guennouni, C. Rasset-Deloge, B. Carboni, M. Vaultier, Synlett 1992, 581; A. Kamabuchi, N. Miyaura, A. Suzuki, Tetrahedron Lett. 1993, 34, 4827; M. Shimizu, T. Kurahashi, T. Hiyama, Synlett 2001, 1006; J. Renoud, C.-D. Graf, L. Oberer. Angew. Chem. 2000, 112, 3231; Angew. Chem. Int. Ed. 2000, 39, 3101; F. Carreaux, F. Posseme, B. Carboni, A. Arrieta, B. Lecea, F. P. Cossio, J. Org. Chem. 2002, 67, 9153.
15. N. Guennouni, C. Rasset-Deloge, B. Carboni, M. Vaultier, Synlett 1992, 581; A. Kamabuchi, N. Miyaura, A. Suzuki, Tetrahedron Lett. 1993, 34, 4827; M. Shimizu, T. Kurahashi, T. Hiyama, Synlett 2001, 1006; J. Renoud, C.-D. Graf, L. Oberer. Angew. Chem. 2000, 112, 3231; Angew. Chem. Int. Ed. 2000, 39, 3101; F. Carreaux, F. Posseme, B. Carboni, A. Arrieta, B. Lecea, F. P. Cossio, J. Org. Chem. 2002, 67, 9153.
16. N. Guennouni, C. Rasset-Deloge, B. Carboni, M. Vaultier, Synlett 1992, 581; A. Kamabuchi, N. Miyaura, A. Suzuki, Tetrahedron Lett. 1993, 34, 4827; M. Shimizu, T. Kurahashi, T. Hiyama, Synlett 2001, 1006; J. Renoud, C.-D. Graf, L. Oberer. Angew. Chem. 2000, 112, 3231; Angew. Chem. Int. Ed. 2000, 39, 3101; F. Carreaux, F. Posseme, B. Carboni, A. Arrieta, B. Lecea, F. P. Cossio, J. Org. Chem. 2002, 67, 9153.
17. For previous reports on cobalt-catalyzed reactions see: G. Hilt, F.X. du Mesnil, S. Lüers, Angew. Chem. 2001, 113, 408; Angew. Chem. Int. Ed. 2001, 40, 387; G. Hilt, K. I. Smolko, Synlett 2002, 1081.
18. For previous reports on cobalt-catalyzed reactions see: G. Hilt, F.X. du Mesnil, S. Lüers, Angew. Chem. 2001, 113, 408; Angew. Chem. Int. Ed. 2001, 40, 387; G. Hilt, K. I. Smolko, Synlett 2002, 1081.
19. For previous reports on cobalt-catalyzed reactions see: G. Hilt, F.X. du Mesnil, S. Lüers, Angew. Chem. 2001, 113, 408; Angew. Chem. Int. Ed. 2001, 40, 387; G. Hilt, K. I. Smolko, Synlett 2002, 1081.
20. 4 was used as reducing agent for the generation of the active cobalt catalyst, side reactions such as the reduction of the triple bond were observed.
21. The regioselectivity can be explained by steric effects as well as by an insertion of the alkynylboron derivative into the intermediate cobaltacycle in terms of a Michael addition.
22. Traces of a side product could be detected by GC and GCMS, which could be either a regioisomer or a double-bond isomer (1,3-cyclohexadiene derivative).
23. Traces of water should be present so the reaction can reach completion within 5 minutes.