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DOI: 10.1055/s-0030-1260954
Copper-Mediated Aryl Amination: In Situ Generation of an Active Copper(I) Species
Publication History
Publication Date:
14 July 2011 (online)
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Abstract
We have developed novel conditions for copper-mediated aryl amination by using a combination of easy-to-handle and inexpensive Cu(OAc)2˙H2O and phenylhydrazine.
Key words
amine - aryl amination - copper - phenylhydrazine - reductant
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1a
Ley SV.Thomas AW. Angew. Chem. Int. Ed. 2003, 42: 5400 -
1b
Kunz K.Scholz U.Ganzer D. Synlett 2003, 2428 -
1c
Evano G.Blanchard N.Toumi M. Chem. Rev. 2008, 108: 3054 -
1d
Ma D.Cai Q. Acc. Chem. Res. 2008, 41: 1450 -
1e
Monnier F.Taillefer M. Angew. Chem. Int. Ed. 2009, 48: 6954 -
1f
Rao H.Fu H. Synlett 2011, 745 -
2a
Ullmann F. Ber. Dtsch. Chem. Ges. 1903, 36: 2382 -
2b
Goldberg I. Ber. Dtsch. Chem. Ges. 1906, 39: 1691 -
3a
Guram AS.Buchwald SL. J. Am. Chem. Soc. 1994, 116: 7901 -
3b
Guram AS.Rennels RA.Buchwald SL. Angew. Chem. Int. Ed. 1995, 34: 1348 -
3c
Peat AJ.Buchwald SL. J. Am. Chem. Soc. 1996, 118: 1028 -
3d
Wolfe JP.Rennels RA.Buchwald SL. Tetrahedron 1996, 52: 7525 -
3e
Wolfe JP.Åhman J.Sadighi JP.Singer RA.Buchwald SL. Tetrahedron Lett. 1997, 38: 6367 -
3f
Wolfe JP.Buchwald SL. Tetrahedron Lett. 1997, 38: 6359 -
3g
Wolfe JP.Wagaw S.Marcoux J.-F.Buchwald SL. Acc. Chem. Res. 1998, 31: 805 -
3h
Harris MC.Geis O.Buchwald SL. J. Org. Chem. 1999, 64: 6019 -
3i
Yang B.Buchwald SL. J. Organomet. Chem. 1999, 576: 125 -
3j
Wolfe JP.Buchwald SL. J. Org. Chem. 2000, 65: 1144 -
3k
Wolfe JP.Tomori H.Sadighi JP.Yin J.Buchwald SL.
J. Org. Chem. 2000, 65: 1158 -
3l
Yin J.Buchwald SL. Org. Lett. 2000, 2: 1101 -
3m
Ali M.Buchwald SL.
J. Org. Chem. 2001, 66: 2560 -
3n
Huang X.Buchwald SL. Org. Lett. 2001, 3: 3417 -
3o
Zhang X.Harris MC.Sadighi JP.Buchwald SL. Can. J. Chem. 2001, 79: 1799 -
3p
Gaertzen O.Buchwald SL. J. Org. Chem. 2002, 67: 465 -
3q
Harris MC.Huang X.Buchwald SL. Org. Lett. 2002, 4: 2885 -
3r
Muci AR.Buchwald SL. Top. Curr. Chem. 2002, 219: 131 -
3s
Yin J.Buchwald SL. J. Am. Chem. Soc. 2002, 124: 6043 -
3t
Enguehard C.Allouchi H.Gueiffier A.Buchwald SL. J. Org. Chem. 2003, 68: 4367 -
3u
Charles MD.Schultz P.Buchwald SL. Org. Lett. 2005, 7: 3965 -
3v
Anderson KW.Tundel RE.Ikawa T.Altman RA.Buchwald SL. Angew. Chem. Int. Ed. 2006, 45: 6523 -
3w
Klingensmith L.Strieter ER.Barder TE.Buchwald SL. Organometallics 2006, 25: 82 -
3x
Shekhar S.Ryberg P.Hartwig JF.Mathew JS.Blackmond DG.Strieter ER.Buchwald SL. J. Am. Chem. Soc. 2006, 128: 3584 -
3y
Strieter ER.Buchwald SL. Angew. Chem. Int. Ed. 2006, 45: 925 -
3z
Biscoe MR.Barder TE.Buchwald SL. Angew. Chem. Int. Ed. 2007, 46: 7232 -
4a
Ikawa T.Barder TE.Biscoe MR.Buchwald SL. J. Am. Chem. Soc. 2007, 129: 13001 -
4b
Fors BP.Krattiger P.Strieter ER.Buchwald SL. Org. Lett. 2008, 10: 3505 -
4c
Surry DS.Buchwald SL. Angew. Chem. Int. Ed. 2008, 47: 6338 -
4d
Henderson JL.Mcdermott SM.Buchwald SL. Org. Lett. 2010, 12: 4438 -
4e
Noel T.Naber JR.Hartman RL.Mcmullen JP.Jensen KF.Buchwald SL. Chem. Sci. 2011, 2: 287 -
4f
Surry DS.Buchwald SL. Chem. Sci. 2011, 2: 27 -
5a
Kiyomori A.Marcoux J.-F.Buchwald SL. Tetrahedron Lett. 1999, 40: 2657 -
5b
Klapars A.Antilla JC.Huang X.Buchwald SL. J. Am. Chem. Soc. 2001, 123: 7727 -
5c
Wolter M.Klapars A.Buchwald SL. Org. Lett. 2001, 3: 3803 -
5d
Antilla JC.Klapars A.Buchwald SL. J. Am. Chem. Soc. 2002, 124: 11684 -
5e
Job GE.Buchwald SL. Org. Lett. 2002, 4: 3703 -
5f
Klapars A.Huang X.Buchwald SL. J. Am. Chem. Soc. 2002, 124: 7421 -
5g
Kwong F.Klapars A.Buchwald SL. Org. Lett. 2002, 4: 581 -
5h
Jiang L.Job GE.Klapars A.Buchwald SL. Org. Lett. 2003, 5: 3667 -
5i
Kwong F.Buchwald SL. Org. Lett. 2003, 5: 793 -
5j
Antilla JC.Baskin JM.Barder TE.Buchwald SL. J. Org. Chem. 2004, 69: 5578 -
5k
Klapars A.Parris S.Anderson KW.Buchwald SL. J. Am. Chem. Soc. 2004, 126: 3529 -
5l
Strieter ER.Blackmond DG.Buchwald SL. J. Am. Chem. Soc. 2005, 127: 4120 -
5m
Altman RA.Buchwald SL. Org. Lett. 2006, 8: 2779 -
5n
Martin R.Rivero MR.Buchwald SL. Angew. Chem. Int. Ed. 2006, 45: 7079 -
5o
Shafir A.Buchwald SL. J. Am. Chem. Soc. 2006, 128: 8742 -
5p
Altman RA.Buchwald SL. Org. Lett. 2007, 9: 643 -
5q
Jones CP.Anderson KW.Buchwald SL. J. Org. Chem. 2007, 72: 7968 -
5r
Martin R.Larsen CH.Cuenca A.Buchwald SL. Org. Lett. 2007, 9: 3379 -
5s
Strieter ER.Bhayana B.Buchwald SL. J. Am. Chem. Soc. 2009, 131: 78 -
5t
Surry DS.Buchwald SL. Chem. Sci. 2010, 1: 13 -
6a
Paul F.Patt J.Hartwig JF. J. Am. Chem. Soc. 1994, 116: 5969 -
6b
Louie J.Hartwig JF. Tetrahedron Lett. 1995, 36: 3609 -
6c
Driver MS.Hartwig JF. J. Am. Chem. Soc. 1996, 118: 7217 -
6d
Hartwig JF.Richards S.Baranano D.Paul F. J. Am. Chem. Soc. 1996, 118: 3626 -
6e
Louie J.Hartwig JF. Angew. Chem. Int. Ed. 1996, 35: 2359 -
6f
Driver MS.Hartwig JF. J. Am. Chem. Soc. 1997, 119: 8232 -
6g
Hartwig JF. Synlett 1997, 329 -
6h
Louie J.Driver MS.Hamann BC.Hartwig JF. J. Org. Chem. 1997, 62: 1268 -
6i
Hamann BC.Hartwig JF. J. Am. Chem. Soc. 1998, 120: 7369 -
6j
Hartwig JF. Angew. Chem. Int. Ed. 1998, 37: 2047 -
6k
Hartwig JF. Acc. Chem. Res. 1998, 31: 852 -
6l
Shaughnessy KH.Hamann BC.Hartwig JF. J. Org. Chem. 1998, 63: 6546 -
6m
Hartwig JF.Kawatsura M.Hauck SI.Shaughnessy KH.Alcazar-Roman LM. J. Org. Chem. 1999, 64: 5575 -
6n
Alcazar-Roman LM.Hartwig JF.Rheingold AL.Liable-Sands LM.Guzei IA. J. Am. Chem. Soc. 2000, 122: 4618 -
6o
Stauffer SR.Lee S.Stambuli JP.Hauck SI.Hartwig JF. Org. Lett. 2000, 2: 1423 -
6p
Lee S.Jorgensen M.Hartwig JF. Org. Lett. 2001, 3: 2729 -
6q
Kuwano R.Utsunomiya M.Hartwig JF. J. Org. Chem. 2002, 67: 6479 -
6r
Hartwig JF. Acc. Chem. Res. 2008, 41: 1534 -
7a
Ma D.Jiang J. Tetrahedron: Asymmetry 1998, 9: 1137 -
7b
Ma D.Zhang Y.Yao J.Wu S.Tao F. J. Am. Chem. Soc. 1998, 120: 12459 -
7c
Ma D.Xia C. Org. Lett. 2001, 3: 2583 -
7d
Ma D.Cai Q.Zhang H. Org. Lett. 2003, 5: 2453 -
7e
Ma D.Xia C.Jiang J.Zhang J.Tang W. J. Org. Chem. 2003, 68: 442 -
7f
Ma D.Cai Q. Synlett 2004, 128 -
7g
Cai Q.Zhu W.Zhang H.Zhang Y.Ma D. Synthesis 2005, 496 -
7h
Zhang H.Cai Q.Ma D.
J. Org. Chem. 2005, 70: 5164 -
7i
He G.Wang J.Ma D. Org. Lett. 2007, 9: 1367 -
7j
Zou B.Yuan Q.Ma D. Angew. Chem. Int. Ed. 2007, 46: 2598 -
7k
Guo L.Li B.Huang W.Pei G.Ma D. Synlett 2008, 1833 -
7l
Diao X.Wang Y.Jiang Y.Ma D. J. Org. Chem. 2009, 74: 7974 -
7m
Gan J.Ma D. Org. Lett. 2009, 11: 2788 -
7n
Wang H.Jiang Y.Gao K.Ma D. Tetrahedron 2009, 65: 8956 -
7o
Lu X.Shi L.Zhang H.Jiang Y.Ma D. Tetrahedron 2010, 66: 5714 -
7p
Maurer S.Liu W.Zhang X.Jiang Y.Ma D. Synlett 2010, 976 -
8a
Yamada K.Kubo T.Tokuyama H.Fukuyama T. Synlett 2002, 231 -
8b
Okano K.Tokuyama H.Fukuyama T. Org. Lett. 2003, 5: 4987 -
8c
Kubo T.Katoh C.Yamada K.Okano K.Tokuyama H.Fukuyama T. Tetrahedron 2008, 64: 11230 -
8d
Okano K.Fukuyama T.Tokuyama H. J. Synth. Org. Chem., Jpn. 2010, 68: 1036 -
8e
Noji T.Okano K.Fukuyama T.Tokuyama H. Org. Synth. 2011, 88: 388 -
9a
Yamada K.Kurokawa T.Tokuyama H.Fukuyama T. J. Am. Chem. Soc. 2003, 125: 6630 -
9b
Okano K.Tokuyama H.Fukuyama T. J. Am. Chem. Soc. 2006, 128: 7136 -
9c
Okano K.Tokuyama H.Fukuyama T. Chem. Asian J. 2008, 3: 296 -
9d
Okano K.Mitsuhashi N.Tokuyama H. Chem. Commun. 2010, 46: 2641 - Reductions of Cu(II) salts with phenylhydrazine have been used for cyclopropanation:
-
10a
Aratani T. Pure Appl. Chem. 1985, 57: 1839 -
10b
Lowenthal R.Abiko A.Masamune S. Tetrahedron Lett. 1990, 31: 6005 -
10c
Glos M.Reiser O. Org. Lett. 2000, 2: 2045 - The reductions have also been used to generate aryl radicals:
-
10d
Varea T.González-Núñez ME.Rodrigo-Chiner J.Asensio G. Tetrahedron Lett. 1989, 30: 4709 -
10e
Briquet A.Hansen H. Helv. Chim. Acta 1994, 77: 1577 - 12 A possibility that amines might
work as a reductant has been reported:
Qin W.Kakusawa N.Wu Y.Yasuike S.Kurita J. Chem. Pharm. Bull. 2009, 57: 436
References and Notes
We reported that the aryl amination reaction with Cu(OAc)2 did not proceed in DMF (ref. 8). DMSO might work as a reductant under these conditions.
13Typical Procedure: A solution of copper(II) acetate monohydrate (0.40 mmol) and amine (4.0 mmol) in DMSO (1 mL) was stirred for 30 min at r.t., whereupon phenylhydrazine (0.20 mmol) was added. After stirring for 30 min, aryl iodide (1.0 mmol) was added to the solution. The reaction mixture was stirred for 30 min, and the solution was warmed to 90 ˚C. After stirring for 23 h at the same temperature, the solution was cooled to r.t. and diluted with EtOAc. The solution was washed with aq ammoniacal sodium chloride (3 ×). The combined aqueous layer was extracted with EtOAc (3 ×). The combined organic layer was washed with brine, dried over Na2SO4, and concentrated under reduced pressure. The residue was purified by column chromatography to give the corresponding aniline.