Communication
ChemComm
1
9
Table 3 Fluorination of various substrates with CsF in the presence of 1
after 24 h of reaction in DMF (140 1C) and under solvent-free conditions
failed to observe ( F NMR and GC-MS) the formation of 2- and
4-FC NO from the corresponding bromo derivatives and
(Ph CuF] or [(Ph P) CuF]/KF, following the procedure reported
6
H
4
2
[
3
P)
3
3
3
(180 1C)
in: I. S. Antipin, A. I. Vigalok and A. I. Konovalov, Zh. Org. Khim.,
1991, 27, 1577.
P. S. Fier and J. F. Hartwig, J. Am. Chem. Soc., 2012, 134, 10795.
Substrate
T, 1C
Product
Yield, % on 1
9
1
C
C
C
C
6
6
6
6
H
H
H
H
5
5
5
5
Cl
Br
I
140
C
C
C
C
6
6
6
6
H
H
H
H
5
5
5
5
F
F
F
F
620
890
10
520
o10
300
20
0 For intramolecular versions of this reaction, see: (a) A. Casitas,
M. Canta, M. Sola, M. Costas and X. Ribas, J. Am. Chem. Soc., 2011,
133, 19386; (b) X. Mu, H. Zhang, P. Chen and G. Liu, Chem. Sci.,
2014, 5, 275.
11 (a) D. A. Watson, M. Su, G. Teverovskiy, Y. Zhang, J. Garcia-Fortanet,
T. Kinzel and S. L. Buchwald, Science, 2009, 325, 1661; (b) H. G. Lee,
P. J. Milner and S. L. Buchwald, Org. Lett., 2013, 15, 5602; (c) H. G. Lee,
P. J. Milner and S. L. Buchwald, J. Am. Chem. Soc., 2014, 136, 3792.
12 S. L. Fraser, M. Yu. Antipin, V. N. Khroustalyov and V. V. Grushin,
J. Am. Chem. Soc., 1997, 119, 4769.
1
80
140
80
140
80
1
1
OTf
140
180
140
4
-CH
-CF
3
C
6
H
4
Cl
Cl
4-CH
4-CF
3
C
6
H
4
F
F
40
20
4
3
C
6
H
4
3
C
6
H
4
1
140
140
80
80
20
40
3
1
-CF
-C10
3
C
6
H
Cl
4
Cl
3-CF
1-C10
3
C
6
H
F
4
F
13 M. F. Semmelhack and A. Chlenov, Top. Organomet. Chem., 2004,
H
7
H
7
7
, 43.
4 (a) J. Miller, Aromatic Nucleophilic Substitution, Elsevier, London,
968; (b) F. Terrier, Modern Nucleophilic Aromatic Substitution, Wiley-
1
1
19
0
See the ESI for details. Yields were determined by F NMR with 4,4 -
difluorobiphenyl as an internal standard.
1
VCH, Weinheim, 2013.
5 (a) R. P. Houghton, R. Price and M. Voyle, J. Chem. Soc., Chem.
Commun., 1980, 884; (b) R. P. Houghton, M. Voyle and R. Price,
J. Chem. Soc., Perkin Trans. 1, 1984, 925; (c) L. I. Goryunov,
V. V. Litvak and V. D. Shteingarts, Izv. Sib. Otd. Akad. Nauk SSSR,
Ser. Khim. Nauk, 1985, 1, 132; (d) L. I. Goryunov, V. V. Litvak and
V. D. Shteingarts, Zh. Org. Khim., 1987, 23, 1230; (e) M. Otsuka,
K. Endo and T. Shibata, Chem. Commun., 2010, 46, 336; ( f ) M. Otsuka,
H. Yokoyama, K. Endo and T. Shibata, Synlett, 2010, 2601; (g) Y. Imazaki,
E. Shirakawa, R. Ueno and T. Hayashi, J. Am. Chem. Soc., 2012,
stability, and activity. The reaction exhibits excellent regio- and
chemoselectivity. Given the extreme scarcity of methods for
nucleophilic fluorination of unactivated aryl halides, the find-
ing reported herein may become a new point of growth in the
area of synthesis of fluoroaromatic compounds.
We thank Drs J. Benet-Buchholz and E. Martin for X-ray
studies. This work was supported by the ICIQ Foundation and
the Spanish Government (Grant CTQ 2011-25418 and Severo
Ochoa Excellence Accreditation 2014-2018 SEV-2013-0319).
1
34, 14760; (h) J. W. Walton and J. M. J. Williams, Chem. Commun.,
2015, 51, 2786; (i) for an overview of C–F activation reactions of
Z -coordinated fluoroarenes, see: H. Amii and K. Uneyama, Chem.
6
Rev., 2009, 109, 2119.
6 See ESI† for details.
1
F.M.M. is thankful to the Government of Spain (MINECO) for 17 V. V. Grushin and W. J. Marshall, Organometallics, 2008, 27, 4825.
1
8 H. Aneetha, M. Jim ´e nez-Tenorio, M. C. Puerta, P. Valerga, V. N.
Sapunov, R. Schmid, K. Kirchner and K. Mereiter, Organometallics,
the FPI PhD Scholarship (BES-2012-054922). E.O.G. thanks ICIQ
for the support of her summer stay at ICIQ.
2002, 21, 5334.
1
2
9 J. Huang, E. D. Stevens, S. P. Nolan and J. L. Petersen, J. Am. Chem.
Soc., 1999, 121, 2674.
0 CCDC 1063666 contains the supplementary crystallographic data for
Notes and references
1
For selected monographs, see: (a) J. H. Clark, D. Wails and T. W.
Bastock, Aromatic Fluorination, CRC Press, Boca Raton, FL, 1996; 21 J. L. Neumeyer and J. G. Cannon, J. Org. Chem., 1961, 26, 4681.
b) P. Kirsch, Modern Fluoroorganic Chemistry, Wiley, Weinheim, 22 R. H. Crabtree, Chem. Rev., 2015, 115, 127.
2 4
[Cp*Ru(PhNMe )]BF .
(
2
2
004; (c) K. Uneyama, Organofluorine Chemistry, Blackwell, Oxford, 23 (a) S. Erhardt, V. V. Grushin, A. H. Kilpatrick, S. A. Macgregor,
006; (d) I. Ojima, Fluorine in Medicinal Chemistry and Chemical
W. J. Marshall and D. C. Roe, J. Am. Chem. Soc., 2008, 130, 4828;
(b) A. V. Ushkov and V. V. Grushin, J. Am. Chem. Soc., 2011, 133,
10999; (c) F. M. Miloserdov, C. L. McMullin, M. Mart ´ı nez Belmonte,
J. Benet-Buchholz, V. I. Bakhmutov, S. A. Macgregor and V. V. Grushin,
Organometallics, 2014, 33, 736.
Biology, Wiley-Blackwell, Chichester, U.K., 2009.
2
3
G. Balz and G. Schiemann, Chem. Ber., 1927, 60, 1186.
For a recent review, see: G. W. Gribble, in Name Reactions for
Functional Group Transformations, ed. J. J. Li, John Wiley & Sons,
Hoboken, New Jersey, 2007, p. 552.
For an excellent review of aromatic diazofluorination reactions before
the Balz–Schiemann work, see: R. E. Banks and J. C. Tatlow,
24 (a) X. D. He, B. Chaudret, F. Dahan and Y.-S. Huang, Organometallics,
1991, 10, 970; (b) U. Koelle, M. H. Wang and G. Raabe, Organometallics,
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4
2
J. Fluorine Chem., 1986, 33, 71.
(a) V. V. Grushin, Chem. – Eur. J., 2002, 8, 1006; (b) V. V. Grushin,
Acc. Chem. Res., 2010, 43, 160.
S. D. Taylor, C. C. Kotoris and G. Hum, Tetrahedron, 1999, 55, 12431 27 W. J. Koros, J. Wang and R. M. Felde, J. Appl. Polym. Sci., 1981,
and references cited therein. 26, 2805.
There has been a renaissance in electrophilic aromatic fluorination 28 We were initially puzzled by the reproducible formation of a black
25 D. Mendoza-Espinosa, B. Donnadieu and G. Bertrand, J. Am. Chem.
Soc., 2010, 132, 7264.
26 T. Fujimoto and T. Ritter, Org. Lett., 2015, 17, 544.
5
6
7
research in the past decade, e.g., see: M. G. Campbell and T. Ritter,
Chem. Rev., 2015, 115, 612.
(a) V. Grushin, US Pat., 7202388, 2007, filed October 2005;
precipitate and lack of fluorination, signaling the presence of O
reactions conducted under argon in closed FEP tubes. The report
of Koros et al. provided a rationale for these observations. We
also found that keeping FEP reactors in an argon-filled glove-box
for a few days prior to use for the fluorination resulted in desorp-
2
in
27
8
(
(
b) V. Grushin, US Pat. Application Publ., US2006/0074261 A1, 2006;
8a,b
c) After the patent application
was filed, it was reported in a PhD
NO
F (trace) after
(16%) after 8 h, respectively. See: D. S. Laitar, 29 A. Z. Kreindlin and M. I. Rybinskaya, Russ. Chem. Rev., 2004, 73, 417.
Dissertation (J. P. Sadighi, Supervisor), MIT, 2006, pp. 35–36; (d) We 30 G. C. Finger and C. W. Kruse, J. Am. Chem. Soc., 1956, 78, 6034.
Thesis that 1-iodonaphthalene and strongly activated 4-IC
react with [(SICy)CuF] in DMF at 100 1C to give 1-C10
0 h and 4-FC NO
6
H
4
2
2
tion of O from the polymer and, consequently, slower catalyst
H
7
deactivation.
2
6
H
4
2
Chem. Commun.
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