Iron/Copper-Cocatalyzed Ullmann N,O-Arylation Using FeCl₃, CuO, and rac-1,1′-Binaphthyl-2,2′-diol

Abstract

We have developed an efficient and inexpensive bimetallic catalyst FeCl₃, CuO, and rac-BINOL that could promote N,O-arylation of aliphatic, arylamines, and phenols. The cross-coupling reaction conditions have high tolerance of various functional groups. This versatile and efficient iron/copper-cocatalyst can widely be used in the synthesis of the compounds containing ­(aryl)C-N or (aryl)C-O(aryl) bond.

Key words

copper - iron - cross-coupling - N-arylation - O-arylation

References and Notes

• 1a Ullmann F. Ber. Dtsch. Chem. Ges.  1903,  36:  2389 
• 1b Ullmann F. Ber. Dtsch. Chem. Ges.  1904,  37:  853 
• 2 Ley SV. Thomas AW. Angew. Chem. Int. Ed.  2003,  42:  5400 
• 3a Klapars A. Antilla JC. Huang X. Buchwald SL. J. Am. Chem. Soc.  2001,  123:  7727 
• 3b Antilla JC. Klapars A. Buchwald SL. J. Am. Chem. Soc.  2002,  124:  11684 
• 3c Antilla JC. Baskin JM. Barder TE. Buchwald SL. J. Org. Chem.  2004,  69:  5578 
• 4a Gujadhur RK. Bates CG. Venkataraman D. Org. Lett.  2001,  3:  4315 
• 4b van Allen D. Venkataraman D. J. Org. Chem.  2003,  68:  4590 
• 5a Kwong FY. Klapars A. Buchwald SL. Org. Lett.  2002,  4:  581 
• 5b Chen Y.-J. Chen H.-H. Org. Lett.  2006,  8:  5609 
• 5c Kwong FY. Buchwald SL. Org. Lett.  2003,  5:  793 
• 6a Ma D. Zhang Y. Yao J. Wu S. Tao F. J. Am. Chem. Soc.  1998,  120:  12459 
• 6b Ma D. Xia C. Org. Lett.  2001,  3:  2583 
• 6c Ma D. Cai Q. Zhang H. Org. Lett.  2003,  5:  2453 
• 6d Ma D. Cai Q. Org. Lett.  2003,  5:  3799 
• 6e Ma D. Cai Q. Synlett  2004,  128 
• 6f Pan X. Cai Q. Ma D. Org. Lett.  2004,  6:  1809 
• 6g Zhu W. Ma D. Chem. Commun.  2004,  888 
• 6h Ma D. Liu F. Chem. Commun.  2004,  1934 
• 6i Zhang H. Cai Q. Ma D. J. Org. Chem.  2005,  70:  5164 
• 6j Guo X. Rao H. Fu H. Jiang Y. Zhao Y. Adv. Synth. Catal.  2006,  348:  2197 
• 7a Cristau H.-J. Cellier PP. Spindler J.-F. Taillefer M. Eur. J. Org. Chem.  2004,  695 
• 7b Cristau H.-J. Cellier PP. Spindler J.-F. Taillefer M. Chem. Eur. J.  2004,  10:  5607 
• 8 Zhang S. Zhang D. Liebeskind LS. J. Org. Chem.  1997,  62:  2312 
• 9a Kelkar AA. Patil NM. Chaudhari RV. Tetrahedron Lett.  2002,  43:  7143 
• 9b Gajare AS. Toyota K. Yoshifuji M. Yoshifuji F. Chem. Commun.  2004,  1994 
• 10 Yang M. Liu F. J. Org. Chem.  2007,  72:  8969 
• 11a Shafir A. Buchwald SL. J. Am. Chem. Soc.  2006,  128:  8742 
• 11b Lv X. Bao W. J. Org. Chem.  2007,  72:  3863 
• 12a Rao H. Fu H. Jiang Y. Zhao Y. J. Org. Chem.  2005,  70:  8107 
• 12b Rao H. Jin Y. Fu H. Jiang Y. Zhao Y. Chem. Eur. J.  2006,  12:  3636 
• 12c Zhu D. Wang R. Mao J. Xu L. Wu F. Wan B. J. Mol. Catal. A: Chem.  2006,  256:  256 
• 12d Jiang D. Fu H. Jiang Y. Zhao Y. J. Org. Chem.  2007,  72:  672 
• 12e Tanimori S. Ura H. Kirihata M. Eur. J. Org. Chem.  2007,  3977 
• See some recent reports for O-arylation:
• 13a Marcoux J.-F. Doye S. Buchwald SL. J. Am. Chem. Soc.  1997,  119:  10539 
• 13b Buck E. Song ZJ. Tschaen D. Dormer PG. Volante RP. Reider PJ. Org. Lett.  2002,  4:  1623 
• 13c Fagan PJ. Hauptman E. Shapiro R. Casalnuovo A. J. Am. Chem. Soc.  2000,  122:  5043 
• 13d Gujadhur RK. Bates CG. Venkataraman D. Org. Lett.  2001,  3:  4135 
• 13e Cristau HJ. Cellier PP. Hamada S. Spindler JF. Tailefer M. Org. Lett.  2004,  6:  913 
• 13f Jin Y. Liu J. Yin Y. Fu H. Jiang Y. Zhao Y. Synlett  2006,  1564 
• 14 Bolm C. Legros J. Paih JL. Zani L. Chem. Rev.  2004,  104:  6217 
• For recent work dealing with iron-mediated arylations concerning C-C bond formation, see:
• 15a Cahiez G. Avedissian H. Synthesis  1998,  1199 
• 15b Dohle W. Kopp F. Cahiez G. Knochel P. Synlett  2001,  1901 
• 15c Fürstner A. Leitner A. Mendez M. Krause H. J. Am. Chem. Soc.  2002,  124:  13856 
• 15d Bedford RB. Bruce DW. Frost RM. Goodby JW. Hird M. Chem. Commun.  2004,  2822 
• 15e Martin R. Fürstner A. Angew. Chem. Int. Ed.  2004,  43:  3955 
• 15f Nakamura M. Matsuo K. Ito S. Nakamura E. J. Am. Chem. Soc.  2004,  126:  3686 
• 15g Shirakawa E. Yamafumi T. Kimura T. Yamaguchi S. Hayashi T. J. Am. Chem. Soc.  2005,  127:  17164 
• 15h Fürstner A. Martin R. Chem. Lett.  2005,  5:  624 
• 15i Fürstner A. Krause H. Lehmann CW. Angew. Chem. Int. Ed.  2006,  45:  440 
• 16a Taillefer M. Xia N. Ouali A. Angew. Chem. Int. Ed.  2007,  46:  934 
• 16b Song R.-J. Deng C.-L. Xie Y.-X. Li J.-H. Tetrahedron Lett.  2007,  48:  7845 
• 16c Correa A. Bolm C. Angew. Chem. Int. Ed.  2007,  46:  8862 
• 16d Correa A. Garcia Mancheno O. Bolm C. Chem. Soc. Rev.  2008,  37:  1108 
• 16e Correa A. Elmore S. Bolm C. Chem. Eur. J.  2008,  14:  3527 
• 16f Correa A. Bolm C. Adv. Synth. Catal.  2008,  350:  391 

17

General Procedure A: Coupling of Aryl Halides with Amines A flask was charged with FeCl₃ (16 mg, 0.1 mmol), CuO (8 mg, 0.1 mmol), Cs₂CO₃ (651 mg, 2 mmol), BINOL (57 mg, 0.2 mmol), and any remaining solids (amine and/or aryl halide). The flask was evacuated and backfilled with nitrogen (this procedure was repeated five times). Aryl halide (1 mmol, if liquid), amine (1.2 mmol, if liquid), and DMF (2 mL) were added to the flask under nitrogen atmosphere. The mixture was allowed to stir under nitrogen atmosphere at the shown temperature for the indicated period of time in the text (see Tables  [¹] and  [²] ). After cooling to r.t., the mixture was diluted with CH₂Cl₂ (ca. 20 mL), the solution was filtered, and the filter cake was further washed with CH₂Cl₂ (ca. 5 mL). The filtrate was washed with 1 M NaOH (ca. 10 mL). The combined aqueous phase was extracted with CH₂Cl₂ (2 × 10 mL). Organic layers were combined and dried over anhyd Na₂SO₄. The solvent of the filtrate was removed with the aid of a rotary evaporator, and the residue was purified by column chromatography on SiO₂ using PE-EtOAc (60:1 to 10:1) as eluent to provide the desired product.
1-Phenyl-1H-indole (5l):^¹6a yellow oil, yield 88%. ^¹H NMR (300 MHz, CDCl₃): δ = 7.61 (d, 1 H, J = 7.56 Hz), 7.42-7.51 (m, 5 H), 7.25-7.30 (m, 2 H), 7.13 (dd, 2 H, J = 9.60, 1.74 Hz), 6.61 (t, 1 H, J = 3.45 Hz). ^¹³C NMR (75 MHz, CDCl₃): δ = 139.9, 135.9, 129.7, 129.4, 128.1, 126.5, 124.5, 122.5, 121.2, 120.5, 110.6, 103.7. MS (EI): m/z = 193.23 [M⁺].

18

General Procedure B: Coupling of Aryl Halides with Phenols A flask was charged with FeCl₃ (16 mg, 0.1 mmol), CuO (8 mg, 0.1 mmol), Cs₂CO₃ (651 mg, 2 mmol), 1,1′-binaphthyl-2,2′-diol (57 mg, 0.2 mmol), and any remaining solids (phenol and/or aryl halide). The flask was evacuated and backfilled with nitrogen (this procedure was repeated five times). Aryl halide (1 mmol, if liquid), phenol (1.2 mmol, if liquid), and DMF (2 mL) were added to the flask under nitrogen atmosphere. The flask mixture was allowed to stir under nitrogen atmosphere at the shown temperature for the indicated period of time in the text (see Table  [³] ). After cooling to r.t., the mixture was diluted with CH₂Cl₂ (ca. 20 mL), the solution was filtered, and the filter cake was further washed with CH₂Cl₂ (ca. 5 mL). The solvent of the filtrate was removed with the aid of a rotary evaporator, and the residue was purified by column chromatography on SiO₂ using PE or PE-EtOAc (60:1 to 100:1) as eluent to provide the desired product.
1-(4-Chlorophenoxy)-3-methylbenzene (7f):^6d colorless oil, yield 79%. ^¹H NMR (300 MHz, CDCl₃): δ = 7.25 (dd, 2 H, J = 6.87, 2.07 Hz), 7.18 (d, 1 H, J = 7.53 Hz), 6.91 (dd, 3 H, J = 6.84, 2.04 Hz), 6.78 (s, 2 H), 2.31 (s, 3 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 157.0, 156.2, 140.2, 129.8, 129.7, 128.2, 124.6, 120.1, 119.8, 116.1, 21.5. MS (EI): m/z = 218.22 [M⁺].