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DOI: 10.1055/s-2008-1078214
Iron/Copper-Cocatalyzed Ullmann N,O-Arylation Using FeCl3, CuO, and rac-1,1′-Binaphthyl-2,2′-diol
Publikationsverlauf
Publikationsdatum:
22. August 2008 (online)
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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
- Supporting Information for this article is available online:
- Supporting Information
-
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
References and Notes
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+].
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+].