Page 9 of 11
Journal of the American Chemical Society
NMR spectra (1H, 13C, 19F, 31P), HRMS, and IR spectra of all
(22) Francotte, P.; Goffin, E.; Fraikin, P.; Lestage, P.; Van Heugen, J.-
C.; Gillotin, F.; Danober, L.; Thomas, J.-Y.; Chiap, P.; Caignard, D.-H.;
Pirotte, B.; de Tullio, P. J. Med. Chem. 2010, 53, 1700.
(23) Ormazábal-Toledo, R.; Contreras, R.; Tapia, R. A.; Campodónico,
P. R. Org. Biomol. Chem. 2013, 11, 2302.
1
2
3
reaction products are include in the supporting information. “This
material is available free of charge via the Internet at
http://pubs.acs.org.”
4
5
6
7
8
9
(24) Wiedemann, S. H.; Ellman, J. A.; Bergman, R. G. J. Org. Chem.
2006, 71, 1969.
(25) Ikawa, T.; Barder, T. E.; Biscoe, M. R.; Buchwald, S. L. J. Am.
Chem. Soc. 2007, 129, 13001.
(26) Tao, C.-Z.; Li, J.; Fu, Y.; Liu, L.; Guo, Q.-X. Tetrahedron Lett.
2008, 49, 70.
AUTHOR INFORMATION
Corresponding Author
(27) Roughley, S. D.; Jordan, A. M. J. Med. Chem. 2011, 54, 3451.
(28) Henderson, J. L.; Buchwald, S. L. Org. Lett. 2010, 12, 4442.
(29) Hartwig, J. F. Acc. Chem. Res. 2008, 41, 1534.
(30) Barluenga, J.; Bayón, A. M.; Asensio, G. J. Chem. Soc. Chem.
Commun. 1983, 19, 1109.
(31) Wolfe, J. P.; Buchwald, S. L. Tetrahedron Lett. 1997, 38, 6359.
(32) Hoi, K. H.; Organ, M. G. Chem. Eur. J. 2012, 18, 804.
(33) Alcazar-Roman, L. M.; Hartwig, J. F. J. Am. Chem. Soc. 2001,
123, 12905.
(34) Shekhar, S.; Hartwig, J. F. Organometallics 2007, 26, 340.
(35) Schulte II, J.; Tweedie, S. Synlett 2007, 2331.
(36) Singer, R. A.; Doré, M.; Sieser, J. E.; Berliner, M. A. Tetrahedron
Lett. 2006, 47, 3727.
(37) Withbroe, G. J.; Singer, R. A.; Sieser, J. E. Org. Process Res. Dev.
2008, 12, 480.
(38) Crawford, S. M.; Lavery, C. B.; Stradiotto, M. Chem. Eur. J. 2013,
19, 16760.
(39) Kotecki, B. J.; Fernando, D. P.; Haight, A. R.; Lukin, K. A. Org.
Lett. 2009, 11, 947.
(40) Gowrisankar, S.; Sergeev, A. G.; Anbarasan, P.; Spannenberg, A.;
Neumann, H.; Beller, M. J. Am. Chem. Soc. 2010, 132, 11592.
(41) Sodium phenoxide is commercially available but some samples
from some commercial suppliers contain impurities that inhibit the cou-
pling reaction. For example, a reaction containing anhydrous NaOPh from
a new bottle purchased from MP Biomedicals did not produce any prod-
uct, whereas a similar reaction wherein NaOPh generated from phenol and
NaH produced 1 in quantitative yeild. See the supporting information for
more details.
(42) Love, P.; Cohen, R. B.; Taft, R. W. J. Am. Chem. Soc. 1968, 90,
2455.
(43) Erickson, J. A.; McLoughlin, J. I. J. Org. Chem. 1995, 60, 1626.
(44) Podol’skii, A. V.; German, L. S.; Knunyants, I. L. Bull. Acad. Sci.
USSR Div. Chem. Sci. 1967, 16, 1092.
(45) Molloy, Bryan B.; Fuller, Ray W. In Biochemistry Involving Car-
bon-Fluorine Bonds; ACS Symposium Series; AMERICAN CHEMICAL
SOCIETY, 1976; Vol. 28, pp 77–98.
(46) A coupling of an aryl chloride with (trifluoromethyl)pyrrolidine
was reported while this manuscript was under revision. Park, N. H.;
Vinogradova, E. V.; Surry, D. S.; Buchwald, S. L. Angew. Chem. Int. Ed.
2015, 10.1002/anie.201502626.
(47) Lavery, C. B.; Rotta-Loria, N. L.; McDonald, R.; Stradiotto, M.
Adv. Synth. Catal. 2013, 355, 981.
(48) Christmann, U.; Pantazis, D. A.; Benet-Buchholz, J.; McGrady, J.
E.; Maseras, F.; Vilar, R. J. Am. Chem. Soc. 2006, 128, 6376.
(49) Barder, T. E.; Biscoe, M. R.; Buchwald, S. L. Organometallics
2007, 26, 2183.
Notes
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
A provisional patent based on this worked has been filed.
ACKNOWLEDGMENT
We thank the Dow Chemical company and the NIH (GM-55382
and Shared Instrumentation Grant S10-RR027172) for funding.
A.T.B. thanks Rebecca A. Green, Matthew A. Larsen, and Dr.
Patrick S. Fier for helpful conversations.
REFERENCES
(1) The Chemistry of Anilines; Rappoport, Z., Ed.; Wiley, 2007; Vol.
1.
(2) McGrath, N. A.; Brichacek, M.; Njardarson, J. T. J. Chem. Educ.
2010, 87, 1348.
(3) Schiødt, F. V.; Rochling, F. A.; Casey, D. L.; Lee, W. M. N. Engl.
J. Med. 1997, 337, 1112.
(4) Blaser, H.-U. Adv. Synth. Catal. 2002, 344, 17.
(5) Perkin, W. H. Proc. R. Soc. Lond. 1862, 12, 713.
(6) Sousa, M. M.; Melo, M. J.; Parola, A. J.; Morris, P. J. T.; Rzepa, H.
S.; de Melo, J. S. S. Chem. Eur. J. 2008, 14, 8507.
(7) Hartwig, J. F.; Shekhar, S.; Shen, Q.; Barrios-Landeros, F. In
PATAI’S Chemistry of Functional Groups; John Wiley & Sons, Ltd, 2009.
(8) Guengerich, F. P. Chem. Res. Toxicol. 2001, 14, 611.
(9) Wiśniewska-Knypl, J. M.; Jablońska, J. K.; Piotrowski, J. K. Br. J.
Ind. Med. 1975, 32, 42.
(10) French, C. L.; Yaun, S.-S.; Baldwin, L. A.; Leonard, D. A.; Zhao,
X. Q.; Calabrese, E. J. J. Appl. Toxicol. 1995, 15, 167.
(11) Wu, X.; Kannan, S.; Sadagopa Ramanujam, V. M.-; Firoze Khan,
M. J. Toxicol. Environ. Health A 2005, 68, 657.
(12) Bhakta, M.; Hollenberg, P. F.; Wimalasena, K. Chem. Commun.
2005, No. 2, 265.
(13) Fauber, B. P.; de Leon Boenig, G.; Burton, B.; Eidenschenk, C.;
Everett, C.; Gobbi, A.; Hymowitz, S. G.; Johnson, A. R.; Liimatta, M.;
Lockey, P.; Norman, M.; Ouyang, W.; René, O.; Wong, H. Bioorg. Med.
Chem. Lett. 2013, 23, 6604.
(14) Phillips, B.; Cai, R.; Delaney, W.; Du, Z.; Ji, M.; Jin, H.; Lee, J.;
Li, J.; Niedziela-Majka, A.; Mish, M.; Pyun, H.-J.; Saugier, J.; Tirunagari,
N.; Wang, J.; Yang, H.; Wu, Q.; Sheng, C.; Zonte, C. J. Med. Chem. 2014,
57, 2161.
(15) Steinman, M.; Topliss, J. G.; Alekel, R.; Wong, Y.-S.; York, E. E.
J. Med. Chem. 1973, 16, 1354.
(16) Van Oeveren, A.; Pio, B. A.; Tegley, C. M.; Higuchi, R. I.; Wu,
M.; Jones, T. K.; Marschke, K. B.; Negro-Vilar, A.; Zhi, L. Bioorg. Med.
Chem. Lett. 2007, 17, 1523.
(17) Xue, F.; Li, H.; Delker, S. L.; Fang, J.; Martásek, P.; Roman, L. J.;
Poulos, T. L.; Silverman, R. B. J. Am. Chem. Soc. 2010, 132, 14229.
(18) Andersch, W.; Curtis, D.; Guan, S.; Guilhabert-Goya, M.; Royalty,
R. N.; Springer, B.; Thielert, W.; Zhu, H. US201422821, August 14,
2014.
(19) Hell, S.; Belov, V.; Mitronova, G.; Bossi, M.; Moneron, G.; Wurm,
C.; Jakobs, S.; Eggeling, C.; Bierwagen, J.; Meyer, L. US2012135459,
May 31, 2012.
(20) Metais, E.; Sabelle, S. US2006021157, February 2, 2006.
(21) Mimura, H.; Kawada, K.; Yamashita, T.; Sakamoto, T.; Kikugawa,
Y. J. Fluor. Chem. 2010, 131, 477.
(50) Barder, T. E.; Buchwald, S. L. J. Am. Chem. Soc. 2007, 129,
12003.
(51) Maimone, T. J.; Milner, P. J.; Kinzel, T.; Zhang, Y.; Takase, M.
K.; Buchwald, S. L. J. Am. Chem. Soc. 2011, 133, 18106.
(52) See Table S2 in the supporting information for the concentrations
of each reagent and the initial rates used to determine the orders in each
reagent.
(53) Bordwell, F. G.; McCallum, R. J.; Olmstead, W. N. J. Org. Chem.
1984, 49, 1424.
(54) Ferretti, A. C.; Mathew, J. S.; Ashworth, I.; Purdy, M.; Brennan,
C.; Blackmond, D. G. Adv. Synth. Catal. 2008, 350, 1007.
(55) Klinkenberg, J. L.; Hartwig, J. F. J. Am. Chem. Soc. 2010, 132,
11830.
(56) Hartwig, J. F. Inorg. Chem. 2007, 46, 1936.
9
ACS Paragon Plus Environment