Manganese(II) chloride-catalyzed alkylmagnesation of 2-alkynylphenol

Chemistry Letters

Volumn , Issue 8, 1998, Pages 785-786

  Nishimae, Shinji ^a   Inoue, Rie ^a   Shinokubo, Hiroshi ^a   Oshima, Koichiro ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0032327933     PISSN: 03667022     EISSN: None     Source Type: Journal    
DOI: 10.1246/cl.1998.785     Document Type: Article

References (21)

1. J. Tang, K. Okada, H. Shinokubo, and K. Oshima, Tetrahedron. 53, 5061 (1997)
2. H. Yorimitsu, J. Tang, K. Okada, H. Shinokubo, and K. Oshima, Chem. Lett., 1998, 11.
3. In contrast, carbometallation of carbon-carbon triple bonds with organocopper reagents have been studied extensively. P. Knochel, in "Comprehensive Organic Synthesis," ed by B. M. Trost, Pergamon Press, Oxford (1991), Vol 4, Chap. 4.4, p. 865; J. F. Normant, in "Organocopper Reagents," ed by R. J. K. Taylor, Oxford University Press, Oxford (1994), Chap. 11, p. 237; J. F. Normant and A. Alexakis, Synthesis, 1981, 841.
4. In contrast, carbometallation of carbon-carbon triple bonds with organocopper reagents have been studied extensively. P. Knochel, in "Comprehensive Organic Synthesis," ed by B. M. Trost, Pergamon Press, Oxford (1991), Vol 4, Chap. 4.4, p. 865; J. F. Normant, in "Organocopper Reagents," ed by R. J. K. Taylor, Oxford University Press, Oxford (1994), Chap. 11, p. 237; J. F. Normant and A. Alexakis, Synthesis, 1981, 841.
5. In contrast, carbometallation of carbon-carbon triple bonds with organocopper reagents have been studied extensively. P. Knochel, in "Comprehensive Organic Synthesis," ed by B. M. Trost, Pergamon Press, Oxford (1991), Vol 4, Chap. 4.4, p. 865; J. F. Normant, in "Organocopper Reagents," ed by R. J. K. Taylor, Oxford University Press, Oxford (1994), Chap. 11, p. 237; J. F. Normant and A. Alexakis, Synthesis, 1981, 841.
6. 14O: C, 81.44; H, 8.70%.
7. The stereochemistry of the main product, (£)-2-(2-methyl-1-hexenyl)phenol (2a) was determined by the comparison with an authentic sample prepared from benzofuran according to the reported procedure (T. Nguyen and E. Negishi, Tetrahedron Lett., 32, 5903 (1991)). Formula Represented
8. J. J. Eisch and J. H. Merkley, J. Organomet. Chem., 20, P27 (1969); J. J. Eisch, J. H. Merkley, and J. E. Galle, J. Org. Chem., 44, 587 (1979); H. G. Richey, Jr. and F. W. von Rein, J. Organomet. Chem., 20, P32 (1969); H. G. Richey, Jr. and F. W. von Rein, Tetrahedron Lett., 1971, 3777; R. B. Miller and T. Reichenbach, Synth. Commun., 6, 319 (1876); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 91, C1 (1975); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 168, 1 (1979); J. G. Duboudin, B. Jousseaume, and A. Bonakdar, J. Organomet. Chem., 168, 227 (1979); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 168, 233 (1979); P. Kociénski, C. Love, and D. A. Robert, Tetrahedron Lett., 30, 6753 (1989).
9. J. J. Eisch and J. H. Merkley, J. Organomet. Chem., 20, P27 (1969); J. J. Eisch, J. H. Merkley, and J. E. Galle, J. Org. Chem., 44, 587 (1979); H. G. Richey, Jr. and F. W. von Rein, J. Organomet. Chem., 20, P32 (1969); H. G. Richey, Jr. and F. W. von Rein, Tetrahedron Lett., 1971, 3777; R. B. Miller and T. Reichenbach, Synth. Commun., 6, 319 (1876); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 91, C1 (1975); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 168, 1 (1979); J. G. Duboudin, B. Jousseaume, and A. Bonakdar, J. Organomet. Chem., 168, 227 (1979); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 168, 233 (1979); P. Kociénski, C. Love, and D. A. Robert, Tetrahedron Lett., 30, 6753 (1989).
10. J. J. Eisch and J. H. Merkley, J. Organomet. Chem., 20, P27 (1969); J. J. Eisch, J. H. Merkley, and J. E. Galle, J. Org. Chem., 44, 587 (1979); H. G. Richey, Jr. and F. W. von Rein, J. Organomet. Chem., 20, P32 (1969); H. G. Richey, Jr. and F. W. von Rein, Tetrahedron Lett., 1971, 3777; R. B. Miller and T. Reichenbach, Synth. Commun., 6, 319 (1876); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 91, C1 (1975); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 168, 1 (1979); J. G. Duboudin, B. Jousseaume, and A. Bonakdar, J. Organomet. Chem., 168, 227 (1979); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 168, 233 (1979); P. Kociénski, C. Love, and D. A. Robert, Tetrahedron Lett., 30, 6753 (1989).
11. J. J. Eisch and J. H. Merkley, J. Organomet. Chem., 20, P27 (1969); J. J. Eisch, J. H. Merkley, and J. E. Galle, J. Org. Chem., 44, 587 (1979); H. G. Richey, Jr. and F. W. von Rein, J. Organomet. Chem., 20, P32 (1969); H. G. Richey, Jr. and F. W. von Rein, Tetrahedron Lett., 1971, 3777; R. B. Miller and T. Reichenbach, Synth. Commun., 6, 319 (1876); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 91, C1 (1975); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 168, 1 (1979); J. G. Duboudin, B. Jousseaume, and A. Bonakdar, J. Organomet. Chem., 168, 227 (1979); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 168, 233 (1979); P. Kociénski, C. Love, and D. A. Robert, Tetrahedron Lett., 30, 6753 (1989).
12. J. J. Eisch and J. H. Merkley, J. Organomet. Chem., 20, P27 (1969); J. J. Eisch, J. H. Merkley, and J. E. Galle, J. Org. Chem., 44, 587 (1979); H. G. Richey, Jr. and F. W. von Rein, J. Organomet. Chem., 20, P32 (1969); H. G. Richey, Jr. and F. W. von Rein, Tetrahedron Lett., 1971, 3777; R. B. Miller and T. Reichenbach, Synth. Commun., 6, 319 (1876); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 91, C1 (1975); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 168, 1 (1979); J. G. Duboudin, B. Jousseaume, and A. Bonakdar, J. Organomet. Chem., 168, 227 (1979); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 168, 233 (1979); P. Kociénski, C. Love, and D. A. Robert, Tetrahedron Lett., 30, 6753 (1989).
13. J. J. Eisch and J. H. Merkley, J. Organomet. Chem., 20, P27 (1969); J. J. Eisch, J. H. Merkley, and J. E. Galle, J. Org. Chem., 44, 587 (1979); H. G. Richey, Jr. and F. W. von Rein, J. Organomet. Chem., 20, P32 (1969); H. G. Richey, Jr. and F. W. von Rein, Tetrahedron Lett., 1971, 3777; R. B. Miller and T. Reichenbach, Synth. Commun., 6, 319 (1876); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 91, C1 (1975); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 168, 1 (1979); J. G. Duboudin, B. Jousseaume, and A. Bonakdar, J. Organomet. Chem., 168, 227 (1979); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 168, 233 (1979); P. Kociénski, C. Love, and D. A. Robert, Tetrahedron Lett., 30, 6753 (1989).
14. J. J. Eisch and J. H. Merkley, J. Organomet. Chem., 20, P27 (1969); J. J. Eisch, J. H. Merkley, and J. E. Galle, J. Org. Chem., 44, 587 (1979); H. G. Richey, Jr. and F. W. von Rein, J. Organomet. Chem., 20, P32 (1969); H. G. Richey, Jr. and F. W. von Rein, Tetrahedron Lett., 1971, 3777; R. B. Miller and T. Reichenbach, Synth. Commun., 6, 319 (1876); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 91, C1 (1975); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 168, 1 (1979); J. G. Duboudin, B. Jousseaume, and A. Bonakdar, J. Organomet. Chem., 168, 227 (1979); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 168, 233 (1979); P. Kociénski, C. Love, and D. A. Robert, Tetrahedron Lett., 30, 6753 (1989).
15. J. J. Eisch and J. H. Merkley, J. Organomet. Chem., 20, P27 (1969); J. J. Eisch, J. H. Merkley, and J. E. Galle, J. Org. Chem., 44, 587 (1979); H. G. Richey, Jr. and F. W. von Rein, J. Organomet. Chem., 20, P32 (1969); H. G. Richey, Jr. and F. W. von Rein, Tetrahedron Lett., 1971, 3777; R. B. Miller and T. Reichenbach, Synth. Commun., 6, 319 (1876); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 91, C1 (1975); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 168, 1 (1979); J. G. Duboudin, B. Jousseaume, and A. Bonakdar, J. Organomet. Chem., 168, 227 (1979); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 168, 233 (1979); P. Kociénski, C. Love, and D. A. Robert, Tetrahedron Lett., 30, 6753 (1989).
16. J. J. Eisch and J. H. Merkley, J. Organomet. Chem., 20, P27 (1969); J. J. Eisch, J. H. Merkley, and J. E. Galle, J. Org. Chem., 44, 587 (1979); H. G. Richey, Jr. and F. W. von Rein, J. Organomet. Chem., 20, P32 (1969); H. G. Richey, Jr. and F. W. von Rein, Tetrahedron Lett., 1971, 3777; R. B. Miller and T. Reichenbach, Synth. Commun., 6, 319 (1876); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 91, C1 (1975); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 168, 1 (1979); J. G. Duboudin, B. Jousseaume, and A. Bonakdar, J. Organomet. Chem., 168, 227 (1979); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 168, 233 (1979); P. Kociénski, C. Love, and D. A. Robert, Tetrahedron Lett., 30, 6753 (1989).
17. J. J. Eisch and J. H. Merkley, J. Organomet. Chem., 20, P27 (1969); J. J. Eisch, J. H. Merkley, and J. E. Galle, J. Org. Chem., 44, 587 (1979); H. G. Richey, Jr. and F. W. von Rein, J. Organomet. Chem., 20, P32 (1969); H. G. Richey, Jr. and F. W. von Rein, Tetrahedron Lett., 1971, 3777; R. B. Miller and T. Reichenbach, Synth. Commun., 6, 319 (1876); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 91, C1 (1975); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 168, 1 (1979); J. G. Duboudin, B. Jousseaume, and A. Bonakdar, J. Organomet. Chem., 168, 227 (1979); J. G. Duboudin, and B. Jousseaume, J. Organomet. Chem., 168, 233 (1979); P. Kociénski, C. Love, and D. A. Robert, Tetrahedron Lett., 30, 6753 (1989).
18. 2 (0.1 mmol) at 25°C for 10 h provided a mixture of 2a (94%), 4 (11%), and 5 (14%) in addition to the recovered 3 (62%).
19. 2). Further deprotonation followed by protonation could give the terminal acetylenic product, 2-(2-propynyl)phenol.
20. An addition of benzaldehyde (3.0 mmol) at 25°C instead of O°C afforded 2-(1-benzoyl-2-methyl-1-hexenyl)phenol, which could be generated by a Cannizzaro-type reaction, in 70% yield along with 6a (22%).
21. Starting material 7 was recovered in 19% or 23% yield after 30 h or 46 h at 25°C.