Chemical Science
Page 4 of 5
DOI: 10.1039/C6SC03383K
organic fraction was dried over Na2SO4, evaporated and purified by
preparative TLC (EtOAc/hexane) to provide the corresponding products
as white solids.
Innovation Promotion Association CAS (No.2014229), and The
Recruitment Program of Global Experts for financial support. We
gratefully acknowledge The Scripps Research Institute, for
financial support. This work was supported by NSF under the
CCI Center for Selective C−H Functionalization, CHEꢀ1205646,
and Novartis for an unrestricted grant.
35
40
45
50
55
60
65
70
75
80
85
90
95
100
1
For selected reviews on C–H functionalization using transition metals, see:
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5
Table 5 Scope of C–H amination a ,b
O
O
Cu(OAc)2, CuBr,
ArF
ArF
N
N
CsOAc, LiOAc, ligand
X
X
H
H
R1R2NH
+
DMSO, 100 oC, air
H
NR1R2
ArF = 4-(CF3)C6F4
N
2
For Pdꢀcatalyzed C–H functionalizations via various redox manifolds, see:
(a) O. Baudoin, A. Herrbach, F. Guéritte, Angew. Chem., Int. Ed. 2003, 42,
5736ꢀ5740; (b) L. S. Campeau, S. Rousseaux, K. Fagnou, J. Am. Chem.
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L =
5a-5k
4a-4e
1
O
O
O
O
ArF
ArF
ArF
O
N
H
N
H
N
H
N
Me
N
F
N
O
O
5a, 52%
5b, 46%
5c, 57%
O
O
O
For iron catalyzed sp2 and sp3 C–H functionalizations, see: (a) A.
Matsumoto, L. Ilies, E. Nakamura, J. Am. Chem. Soc. 2011, 133, 6557ꢀ
6559; (b) S.; Asako, L. Ilies, E. Nakamura, J. Am. Chem. Soc. 2013, 135,
17755ꢀ17757; (c) R. Shang, L. Ilies, A. Matsumoto, E. Nakamura, J. Am.
Chem. Soc. 2013, 135, 6030ꢀ6032; (d) L. Ilies, T. Matsubara, S. Ichikawa,
S. Asako, E. Nakamura, J. Am. Chem. Soc. 2014, 136, 13126ꢀ13129; (e) R.
Shang, L. Ilies, S. Asako, E. Nakamura, J. Am. Chem. Soc. 2014, 136 ,
14349ꢀ14352; (f) R. Shang, L. Ilies, E. Nakamura, J. Am. Chem.
Soc. 2015, 137, 7660ꢀ7663.
ArF
ArF
ArF
3
N
H
N
H
N
H
Cl
N
F3C
N
N
O
O
O
5d, 51%
5e, 53%
5f, 47%
O
O
O
ArF
O
ArF
ArF
N
H
N
H
N
H
Ph
N
Cl
N
Cl
N
O
4
For recent development of Cuꢀcatalylzed C–H functionalizations, see: (a)
G. Brasche, S. L. Buchwald, Angew. Chem., Int. Ed. 2008, 47, 1932ꢀ1934;
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Me
5g, 55%
5h, 51%
5i, 47%
O
N
O
ArF
ArF
N
N
H
H
Cl
Cl
N
N
Boc
COOEt
5j, 43%
5k, 48%
a
Reaction conditions: 1 (0.1 mmol), 4a-4e (0.3 mmol), Cu(OAc)2 (0.2
10 mmol), CuBr (0.1 mmol), CsOAc (0.2 mmol), LiOAc (0.1 mmol), ligand
(0.05 mmol), DMSO (1.0 mL), 100 oC, air, 6 h. b Isolated yield.
Notes and references
15 a State Key Laboratory of Organometallic Chemistry, Shanghai Institute
of Organic Chemistry, Shanghai 20032, China. E-mail:hxdai@sioc.ac.cn;
b Department of Chemistry, The Scripps Research Institute, 10550 N.
Torrey Pines Road, La Jolla, California 92037, USA;
20 c Department of Chemistry, Innovative Drug Research Center, Shanghai
University, 99 Shangda Road, 200444, China.
† Electronic Supplementary Information (ESI) available: Data for new
compounds and experimental procedures. See DOI: 10.1039/b000000x/
25 ‡ General procedure for Copper Promoted orthoꢀC–H Hydroxylation: To
a 15 mL sealed tube was added substrates 1 (0.1 mmol, 1.0 equiv),
Cu(OPiv)2 (0.15 mmol), CuBr (0.08 mmol), Cs2CO3 (0.15 mmol), 1ꢀAdꢀ
COOH (0.18 mmol), ligand L15 (0.04 mmol) and DMSO (0.5 mL). The
reaction tube was then placed into a preꢀheated oil bath and stirred at 105
30 oC for 6 h under air. Upon completion, EtOAc was added to dilute the
mixture and then washed with NH3·H2O and saturated NaCl(aq). The
5
For few examples of Fe, Co catalyzed C–H functionalizations with a
weakly coordinating DG, see: (a) Q. Chen, L. Ilies, N. Yoshikai, E.
Nakamura, Org. Lett. 2011, 13, 3232ꢀ3234; (b) Q. Chen, L. Ilies, E.
Nakamura, J. Am. Chem. Soc. 2011, 133, 5221ꢀ5223; (c) L. Ilies, E.
Konno, Q. Chen, E. Nakamura, Asian J. Org. Chem. 2012, 1, 142ꢀ145.
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