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Volumn 12, Issue 7, 2010, Pages 1532-1535

Copper-mediated n-heteroarylation of primary sulfonamides: Synthesis of mono-n-heteroaryl sulfonamides

Author keywords

[No Author keywords available]

Indexed keywords

COPPER; CUPROUS IODIDE; IODIDE; SULFONAMIDE;

EID: 77950241664     PISSN: 15237060     EISSN: 15237052     Source Type: Journal    
DOI: 10.1021/ol100263r     Document Type: Article
Times cited : (88)

References (47)
  • 2
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    • Also see ref 8 for other medicinal uses of sulfonamides.
    • (b) Also see ref 8 for other medicinal uses of sulfonamides.
  • 14
    • 0035858723 scopus 로고    scopus 로고
    • For the coupling of aryl halides and sulfonamides under the classic Goldberg reaction conditions see
    • (c) Lam, P. Y. S.; Vincent, G.; Clark, C. G.; Deudon, S.; Jadhav, P. K. Tetrahedron Lett. 2001, 42, 3415-3418. For the coupling of aryl halides and sulfonamides under the classic Goldberg reaction conditions see:
    • (2001) Tetrahedron Lett. , vol.42 , pp. 3415-3418
    • Lam, P.Y.S.1    Vincent, G.2    Clark, C.G.3    Deudon, S.4    Jadhav, P.K.5
  • 15
    • 0037436943 scopus 로고    scopus 로고
    • For examples of catalytic coupling of aryl halides and sulfonamides
    • (d) He, H.; Wu, Y.-J. Tetrahedron Lett. 2003, 44, 3385-3386. For examples of catalytic coupling of aryl halides and sulfonamides
    • (2003) Tetrahedron Lett. , vol.44 , pp. 3385-3386
    • He, H.1    Wu, Y.-J.2
  • 18
    • 71049189682 scopus 로고    scopus 로고
    • During the course of the preparation of this manuscript, the coupling of pyridine derivatives and sulfonamides was repotted: Han, X. Tetrahedron Lett. 2010, 51, 360-362.
    • (2010) Tetrahedron Lett. , vol.51 , pp. 360-362
    • Han, X.1
  • 19
    • 0034738131 scopus 로고    scopus 로고
    • For an example of product inhibition associated with the use of primary sulfonamides
    • For examples of use of 2-aminopyridine as ligands in copper catalysis, see: (a) Fagan, P. J.; Hauptman, E.; Shapiro, R.; Casalnuovo, A. J. Am. Chem. Soc. 2000, 122, 5043-5505 For an example of product inhibition associated with the use of primary sulfonamides see:
    • (2000) J. Am. Chem. Soc. , vol.122 , pp. 5043-5505
    • Fagan, P.J.1    Hauptman, E.2    Shapiro, R.3    Casalnuovo, A.4
  • 22
    • 14844349847 scopus 로고    scopus 로고
    • CuI as additives in the Hiyama and Suzuki cross-coupling of 2-borono and trimediylsilane pyridine, see: (a) Pierrat, P.; Gros, P.; Fort, Y. Org. Lett. 2005, 7, 697-700.
    • (2005) Org. Lett. , vol.7 , pp. 697-700
    • Pierrat, P.1    Gros, P.2    Fort, Y.3
  • 35
    • 77950258220 scopus 로고    scopus 로고
    • The screening results are summarized in Table 1 in the SI.
    • The screening results are summarized in Table 1 in the SI.
  • 42
    • 77950289809 scopus 로고    scopus 로고
    • Typical experimental procedure: A dry vial was cooled to it under nitrogen, and was charged with copper(I) iodide (43.0 mg, 0.23 mmol), potassium carbonate (4.15 mg, 3.0 mmol), and p-toluene sulfonamide (257 mg, 1.50 mmol). Dry DMF (10 mL) was added, followed by ligand 1 (0.071 mL, 0.45 mmol) and 2-bromopyridine (286 mg, 1.80 mmol). The resulting blue suspension was stirred at it for 5 min, then heated to 100 °C for 16 h. The reaction mixture was then cooled to it, diluted with ethyl acetate (75 mL), then transferred to a separatory funnel and washed with 10% aqueous ammonium chloride. The aqueous phase was extracted with ethyl acetate (3 times 60 mL). The combined organic phases were washed with water (3 times 75 mL) and brine then dried over magnesium sulfate. All the volatiles were evaporated, and the resulting residue was purified by silica gel chromatography with a DCM/MeOH gradient.
    • Typical experimental procedure: A dry vial was cooled to it under nitrogen, and was charged with copper(I) iodide (43.0 mg, 0.23 mmol), potassium carbonate (4.15 mg, 3.0 mmol), and p-toluene sulfonamide (257 mg, 1.50 mmol). Dry DMF (10 mL) was added, followed by ligand 1 (0.071 mL, 0.45 mmol) and 2-bromopyridine (286 mg, 1.80 mmol). The resulting blue suspension was stirred at it for 5 min, then heated to 100 °C for 16 h. The reaction mixture was then cooled to it, diluted with ethyl acetate (75 mL), then transferred to a separatory funnel and washed with 10% aqueous ammonium chloride. The aqueous phase was extracted with ethyl acetate (3 times 60 mL). The combined organic phases were washed with water (3 times 75 mL) and brine then dried over magnesium sulfate. All the volatiles were evaporated, and the resulting residue was purified by silica gel chromatography with a DCM/MeOH gradient.
  • 43
    • 16244411305 scopus 로고    scopus 로고
    • Recent experimental and theoretical studies have indicated that the rate-determining step of the arylation of amides with copper is the oxidative addition. We assumed that a similar reaction mechanism is operative: (a) Strieter, E. R.; Blackmond, D. G.; Buchwald, S. L. J. Am. Chem. Soc. 2005, 127, 4120-4125.
    • (2005) J. Am. Chem. Soc. , vol.127 , pp. 4120-4125
    • Strieter, E.R.1    Blackmond, D.G.2    Buchwald, S.L.3


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