A new strategy for deprotonative functionalization of aromatics: Transformations with excellent chemoselectivity and unique regioselectivities using t-Bu-P4 base

Journal of the American Chemical Society

Volumn 125, Issue 27, 2003, Pages 8082-8083

  Imahori, Tatsushi ^a   Kondo, Yoshinori ^a  

^a TOHOKU UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC COMPOUND; BASE; BENZENE DERIVATIVE; BENZOPHENONE; BENZOTHIAZOLE; LEWIS ACID; PYRIDINE DERIVATIVE; TOLUENE; ZINC DERIVATIVE;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL MODIFICATION; CHEMICAL REACTION; CHEMOSENSITIVITY; METHODOLOGY;

EID: 0037668413     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0342300     Document Type: Article

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35. The t-Bu-P4 base shows excellent chemoselectivity in deprotonation in the presence of electrophiles: (a) Kraus, G. A.; Zhang, N.; Verkade, J. G.; Nagarajan, M.; Kisanga, P. B. Org. Lett. 2000, 2, 2409-2410. (b) Pietzonka, T.; Seebach, D. Chem. Ber. 1991, 124, 1837-1843. (c) Pietzonka; T.; Seebach, D. Angew. Chem., Int. Ed. Engl. 1993, 32, 716-717. (d) Leito, I.; Rodima, T.; Koppel, I. A.; Schwesinger, R.; Vlasov, V. M. J. Org. Chem. 1997, 62, 8479-8483. (e) Schlaad, H.; Kukula, H.; Rudloff, J.; Below, I. Macromolecules 2001, 34, 4302-4304.
36. The t-Bu-P4 base shows excellent chemoselectivity in deprotonation in the presence of electrophiles: (a) Kraus, G. A.; Zhang, N.; Verkade, J. G.; Nagarajan, M.; Kisanga, P. B. Org. Lett. 2000, 2, 2409-2410. (b) Pietzonka, T.; Seebach, D. Chem. Ber. 1991, 124, 1837-1843. (c) Pietzonka; T.; Seebach, D. Angew. Chem., Int. Ed. Engl. 1993, 32, 716-717. (d) Leito, I.; Rodima, T.; Koppel, I. A.; Schwesinger, R.; Vlasov, V. M. J. Org. Chem. 1997, 62, 8479-8483. (e) Schlaad, H.; Kukula, H.; Rudloff, J.; Below, I. Macromolecules 2001, 34, 4302-4304.
37. The t-Bu-P4 base shows excellent chemoselectivity in deprotonation in the presence of electrophiles: (a) Kraus, G. A.; Zhang, N.; Verkade, J. G.; Nagarajan, M.; Kisanga, P. B. Org. Lett. 2000, 2, 2409-2410. (b) Pietzonka, T.; Seebach, D. Chem. Ber. 1991, 124, 1837-1843. (c) Pietzonka; T.; Seebach, D. Angew. Chem., Int. Ed. Engl. 1993, 32, 716-717. (d) Leito, I.; Rodima, T.; Koppel, I. A.; Schwesinger, R.; Vlasov, V. M. J. Org. Chem. 1997, 62, 8479-8483. (e) Schlaad, H.; Kukula, H.; Rudloff, J.; Below, I. Macromolecules 2001, 34, 4302-4304.
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39. An interesting reaction of benzothiazole with -Bu-P4 base has been reported in ref 6a, Also, similar chemistry of thiazoles without metallic bases has been developed with 2-(trimethysilyl)thiazoles, see: (a) Pinkerton, F. H.; Thames, S. F. J. Heterocycl, Chem. 1971, 8, 257-259. (b) Dondoni, A, Pure Appl. Chem. 1990, 62, 643-652.
40. An interesting reaction of benzothiazole with -Bu-P4 base has been reported in ref 6a, Also, similar chemistry of thiazoles without metallic bases has been developed with 2-(trimethysilyl)thiazoles, see: (a) Pinkerton, F. H.; Thames, S. F. J. Heterocycl, Chem. 1971, 8, 257-259. (b) Dondoni, A, Pure Appl. Chem. 1990, 62, 643-652.
41. For deprotonative functionalizations of 3-bromopyridine using a metallic base, see: (a) Effenberger, F.; Daub, W. Chem. Ber. 1991, 124, 2119-2125. (b) Gribble, G. W.; Saulnier, M. G. Heterocycles 1993, 35, 151-169.
42. For deprotonative functionalizations of 3-bromopyridine using a metallic base, see: (a) Effenberger, F.; Daub, W. Chem. Ber. 1991, 124, 2119-2125. (b) Gribble, G. W.; Saulnier, M. G. Heterocycles 1993, 35, 151-169.
43. The deprotonative functionalization of pyridazine and pyrimidine using a metallic base has been reported, see: Plé, N.; Turck, A.; Couture, K.; Quéguiner, G. J. Org. Chem. 1995, 60, 3781-3786.
44. Deprotonative functionalizations of azines often have undesirable side reactions: Quéguiner, G.; Marsais, F.; Snieckus, V.; Epsztajin, J. Adv. Heterocycl. Chem. 1991, 52, 187-304.
45. The reaction of pyridazine with benzaldehyde provided benzoyl product 6b′ via deprotonative functionalization and subsequent oxidation, not the expected alcohol.
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48. The deprotonative metalation of 4-bromobenzonitrile with TMP-zincate and subsequent treatment with benzaldehyde yielded 5-bromo-3-phenylphthalide via deprotonative zincation at the 2-position with a trace amount of the 3-adduct: Imahori, T.; Kondo, Y., unpublished data.