A multistep synthesis of 4-nitro-l-ethynylbenzene involving palladium catalysis, conformational analysis, acetal hydrolysis, and oxidative decarbonylation

Journal of Chemical Education

Volumn 76, Issue 1, 1999, Pages 74-75

  Goodwin, Thomas E ^a   Hurst, Eva M ^a   Ross, Ashley S ^a  

^a HENDRIX COLLEGE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0039852457     PISSN: 00219584     EISSN: None     Source Type: Journal    
DOI: 10.1021/ed076p74     Document Type: Article

References (17)

1. Heck, R. F. Palladium Reagents in Organic Synthesis; Academic: New York, 1985. Tsuji, J. Palladium Reagents and Catalysts: Innovations in Organic Synthesis Wiley: New York, 1995.
2. Heck, R. F. Palladium Reagents in Organic Synthesis; Academic: New York, 1985. Tsuji, J. Palladium Reagents and Catalysts: Innovations in Organic Synthesis Wiley: New York, 1995.
3. Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett. 1975, 19, 4467. Alami, M.; Ferri, F.; Linstrumelle, G. Tetrahedron Lett. 1993, 34, 6403. Bleicher, L.; Cosford, N. D. P. Synlett 1995, 1115- Nguefack, J-F.; Bolitt, V.; Sinou, D. Tetrahedron Lett. 1996, 37, 5527.
4. Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett. 1975, 19, 4467. Alami, M.; Ferri, F.; Linstrumelle, G. Tetrahedron Lett. 1993, 34, 6403. Bleicher, L.; Cosford, N. D. P. Synlett 1995, 1115- Nguefack, J-F.; Bolitt, V.; Sinou, D. Tetrahedron Lett. 1996, 37, 5527.
5. Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett. 1975, 19, 4467. Alami, M.; Ferri, F.; Linstrumelle, G. Tetrahedron Lett. 1993, 34, 6403. Bleicher, L.; Cosford, N. D. P. Synlett 1995, 1115- Nguefack, J-F.; Bolitt, V.; Sinou, D. Tetrahedron Lett. 1996, 37, 5527.
6. Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett. 1975, 19, 4467. Alami, M.; Ferri, F.; Linstrumelle, G. Tetrahedron Lett. 1993, 34, 6403. Bleicher, L.; Cosford, N. D. P. Synlett 1995, 1115- Nguefack, J-F.; Bolitt, V.; Sinou, D. Tetrahedron Lett. 1996, 37, 5527.
7. Brisbois, R. G.; Batterman, W. G.; Kragerud, S. R. J. Chem. Educ. 1997, 74, 832.
8. A previous report details the copper-catalyzed coupling of the same alkyne with iodobenzene: Okuro, K.; Furuune, M.; Enna, M.; Miura, M.; Nomura, M. J. Org. Chem. 1993, 58, 4716.
9. We have also carried out this reaction in 100 proof vodka, using a commercial animal deworming medication as the base: Chem. Eng. News 1996, 74(April 15), 34.
10. Alkynes 3 and 4 have previously been prepared via the copper acetylide of compound 1: Harris, M. A.; McMillan, I.; Nayler, J. H. C.; Osborne, N. F.; Pearson, M. J.; Southgate, R. J. Chem. Soc., Perkin Trans. 11976, 1612.
11. a are 10.7 and 3.3 Hz for conformer 2; for conformer 3 they are 3.8 and 2.3 Hz.
12. Eliel, E. L.; Wilen, S. H.; Mander, L. N. Stereochemistry of Organic Compounds; Wiley-Interscience: New York, 1994; pp 749-752.
13. 1H NMR analysis of diastereotopic hydrogens is also discussed: Brisbois, R. G.; Batterman, W. G.; Kragerud, S. R. J. Chem. Educ. 1997, 74, 834.
14. 1H NMR spectroscopy and molecular modeling, see Midland, M. M.; Beck, J. J.; Peters, J. L.; Rennels, R. A.; Asirwatham, G. J. Chem. Educ. 1994, 71, 897.
15. For alternative preparations of alcohol 4 via Pd-catalyzed alkyne coupling, see (a) Bumagin, N. A.; Ponomaryov, A. B.; Beletskaya, I. P. Synthesis 1984, 728. (b) Bumagin, N. A.; Bykov, V. V.; Beletskaya, I. P. Russ. J. Org. Chem. 1995, 31, 348.
16. For alternative preparations of alcohol 4 via Pd-catalyzed alkyne coupling, see (a) Bumagin, N. A.; Ponomaryov, A. B.; Beletskaya, I. P. Synthesis 1984, 728. (b) Bumagin, N. A.; Bykov, V. V.; Beletskaya, I. P. Russ. J. Org. Chem. 1995, 31, 348.
17. For a shorter, alternative synthesis of alkyne 6 via Pd-catalyzed alkyne coupling, see Takahashi, S.; Kuroyama, Y.; Sonogashira, K.; Hagihara, N. Synthesis 1980, 627.