Journal of the American Chemical Society
Article
Chem. 1996, 20, 659−667. (d) Durandetti, M.; Sibille, S.; Ned
Y.; Perichon, J. Synth. Commun. 1994, 24, 145−151. (e) Conan, A.;
Sibille, S.; Dincan, E.; Perichon, J. Chem. Commun. 1990, 48−49.
(f) Folest, J. C.; Perichon, J.; Fauvarque, J. F.; Jutand, A. J. Organomet.
Chem. 1988, 342, 259−261.
(13) For selected electrochemical approaches, see: (a) Durandetti,
́
el
́
ec, J.
2006, 8, 765−768. For recent examples of directed-ortho-metalation/
́
cross-coupling strategy using amides or esters as directors, see:
́
(c) Hurst, T. E.; Macklin, T. K.; Becker, M.; Hartmann, E.; Kugel, W.;
̈
́
Parisienne-La Salle, J.-C.; Batsanov, A. S.; Marder, T. B.; Snieckus, V.
Chem. −Eur. J. 2010, 16, 8155−8161. (d) Quasdorf, K. W.; Riener, M.;
Petrova, K. V.; Garg, N. K. J. Am. Chem. Soc. 2009, 131, 17748−17749.
(e) Alessi, M.; Larkin, A. L.; Ogilvie, K. A.; Green, L. A.; Lai, S.; Lopez,
S.; Snieckus, V. J. Org. Chem. 2007, 72, 1588−1594.
M.; Per
O.; Labbe, E.; Gosmini, C.; Per
562, 255−260. (c) Gomes, P.; Gosmini, C.; Per
2003, 68, 1142−1145. (d) Buriez, O.; Labbe, E.; Per
J. Electroanal. Chem. 2003, 543, 143−151. (e) Gomes, P.; Gosmini,
C.; Perichon, J. Org. Lett. 2003, 5, 1043−1045.
́
ichon, J. Synthesis 2004, 3079−3083. (b) Gomes, P.; Buriez,
ichon, J. J. Electroanal. Chem. 2004,
ichon, J. J. Org. Chem.
ichon, J.
́
́
(30) (a) Klein, A.; Budnikova, Y. H.; Sinyashin, O. G. J. Organomet.
Chem. 2007, 692, 3156−3166. (b) Yakhvarov, D. G.; budnikova, Y. H.;
Sinyashin, O. G. Russ. Chem. Bull. Int. Ed. 2003, 52, 567−569.
(c) Yakhvarov, D. G.; Budnikova, Y. G.; Sinyashin, O. G. Russ. J.
Electrochem. 2003, 39, 1261−1269. (d) Yakhvarov, D. G.; Samieva, E.
G.; Tazeev, D. I.; Budnikova, Y. G. Russ. Chem. Bull. Int. Ed. 2002, 51,
796−804.
(31) (a) Purser, S.; Moore, P. R.; Swallow, S.; Gouverneur, V. Chem.
Soc. Rev. 2008, 37, 320−330. (b) Kirk, K. L. Org. Process Res. Dev.
2008, 12, 305−321.
(32) Under the reaction conditions listed in Scheme 2, the coupling
of 8-bromo-1-octene with ethyl 3-bromobenzoate resulted in a mixture
(46:37:13 ratio based on GC A%) of three olefin isomers. Olefin
isomerization could be suppressed by the addition of 3 equiv of
N, N-diisopropylethylamine. Under these reaction conditions the rate
of product formation was slower, but at partial conversion a single
product was observed by GC analysis of the crude reaction mixture. At
longer reaction times (41 h) a mixture of isomers was again observed
(19:36:16 ratio based on GC A%, accompanied by 24 A%
hydrodehalogenated aryl bromide).
́
́
(14) For selected electrochemical approachs, see ref 11 and
(a) Durandetti, M.; Hardou, L.; Clement, M.; Maddaluno, J. Chem.
Commun. 2009, 4753−4755. (b) Begouin, J. M.; Claudel, S.; Gosmini,
C. Synlett 2009, 3192−3194.
(15) For example, the cross-McMurry reaction: (a) McMurry, J. E.
Chem. Rev. 1989, 89, 1513−1524. (b) Ladipo, F. T. Curr. Org. Chem.
2006, 10, 965−980.
(16) (a) Parshall, G. W. J. Am. Chem. Soc. 1974, 96, 2360−2366.
(b) Nakamura, A.; Otsuka, S. Tetrahedron Lett. 1974, 15, 463−466.
(c) Matsumoto, H.; Inaba, S.; Rieke, R. D. J. Org. Chem. 1983, 48, 840−
843. (d) Yamamoto, T.; Wakabayashi, S.; Osakada, K. J. Organomet.
Chem. 1992, 428, 223−237. (e) Osakada, K.; Yamamoto, T. Coord.
Chem. Rev. 2000, 198, 379−399.
(17) For electron transfer mechanisms, see: (a) Kochi, J. Acc. Chem.
Res. 1974, 7, 351−360. (b) Morrell, D. G.; Kochi, J. K. J. Am. Chem.
Soc. 1975, 97, 7262−7270. (c) Tsou, T. T.; Kochi, J. K. J. Am. Chem.
Soc. 1979, 101, 7547−7560.
(33) (a) Ren, P.; Vechorkin, O.; Allmen, K. v.; Scopelliti, R.; Hu, X.
J. Am. Chem. Soc. 2011, 133, 7084−7095. (b) Molander, G. A.;
Argintaru, O. A.; Aron, I.; Dreher, S. D. Org. Lett. 2010, 12, 5783−
5785. (c) Vechorkin, O.; Proust, V. r.; Hu, X. J. Am. Chem. Soc. 2009,
131, 9756−9766. (d) Vechorkin, O.; Hu, X. Angew. Chem., Int. Ed.
2009, 48, 2937−2940. (e) Strotman, N. A.; Sommer, S.; Fu, G. C.
Angew. Chem., Int. Ed. 2007, 46, 3556−3558. (f) Gonzalez-Bobes, F.;
Fu, G. C. J. Am. Chem. Soc. 2006, 128, 5360−5361. (g) Powell, D. A.;
Maki, T.; Fu, G. C. J. Am. Chem. Soc. 2005, 127, 510−511. (h) Powell,
D. A.; Fu, G. C. J. Am. Chem. Soc. 2004, 126, 7788−7789.
(i) Netherton, M.; Fu, G. Ad. Synth. Catal. 2004, 346, 1525−1532.
(34) For selected examples of Suzuki−Miyaura coupling reactions of
substrates bearing −OH groups that employ excess base, see:
(a) Petronzi, C.; Filosa, R.; Peduto, A.; Monti, M. C.; Margarucci,
L.; Massa, A.; Ercolino, S. F.; Bizzarro, V.; Parente, L.; Riccio, R.; de
Caprariis, P. Eur. J. Med. Chem. 2011, 46, 488−496. (b) Baxendale,
I. R.; Griffiths-Jones, C. M.; Ley, S. V.; Tranmer, G. K. Chem.− Eur. J.
2006, 12, 4407−4416. (c) Handy, S. T.; Zhang, Y.; Bregman, H. J. Org.
(18) Colon, I.; Kelsey, D. R. J. Org. Chem. 1986, 51, 2627−2637.
(19) Amatore, C.; Jutand, A. Organometallics 1988, 7, 2203−2214.
(20) For a review on the Ullmann coupling, see: Hassan, J.;
Sevignon, M.; Gozzi, C.; Schulz, E.; Lemaire, M. Chem. Rev. 2002, 102,
1359−1470.
(21) For examples of L2ArNi(II)X complexes reacting with R−X to
give Ar−R and L2Ni(0), see: (a) Uchino, M.; Yamamoto, A.; Ikeda, S.
́
J. Organomet. Chem. 1970, 24, C63−C64. (b) Folest, J. C.; Perichon,
J.; Fauvarque, J. F.; Jutand, A. J. Organomet. Chem. 1988, 342, 259−
261. (c) Kim, Y.-J.; Sato, R.; Maruyama, T.; Osakada, K.; Yamamoto,
T. Dalton Trans. 1994, 943−948.
(22) (a) Semmelhack, M. F.; Helquist, P. M.; Jones, L. D.
J. Am. Chem. Soc. 1971, 93, 5908−5910. (b) Hegedus, L. S.; Miller,
L. L. J. Am. Chem. Soc. 1975, 97, 459−460. (c) Bradley, J. S.; Connor,
D. E.; Dolphin, D.; Labinger, J. A.; Osborn, J. A. J. Am. Chem. Soc.
1972, 94, 4043−4044.
(23) For a similar proposal involving the coupling of alkyl halides
with π-allyl nickel bromide, see: Hegedus, L. S.; Miller, L. L. J. Am.
Chem. Soc. 1975, 97, 459−460.
(24) The coupling of iodobenzene with iodooctane proceeded in
88% GC yield, iodobenzene with bromooctane in 85% GC yield,
bromobenzene with iodooctane in 77% GC yield, and bromobenzene
with bromooctane in 65% GC yield.
(25) Amatore, M.; Gosmini, C. Chem.−Euro. J. 2010, 16, 5848−5852.
(26) The coupling of 4-chlorobenzonitrile with 1-bromo-3-phenyl-
propane required 2 equiv of the bromoalkane and 20 mol % catalyst
and formed the product with a 57% yield.
(27) For example, the coupling of bromobenzene with 1-
bromooctane in in DMPU with 4,4′-di-tert-butyl-2,2′-dipyridyl (4) at
80 °C failed to consume all starting materials after 42 h.
(28) Ligand prices (Aldrich Chemical Co.): 4,4′-di-tert-butyl-2,2′-
dipyridyl (4) $7.86/g, 4,4′-dimethoxy-bipyridine (6) $23.40/g, 1,10-
phenanthroline (7) $2.66/g.
(29) Coordinating substituents ortho to the halogen, such as −C(O)
R and −CO2R, resulted in quantative hydrodehalogenation of the
bromoarene. These products are best synthesized by a directed-ortho-
metalation/cross-coupling strategy. For metalation using ester and
ketone groups as directors, see: (a) Wunderlich, S.; Knochel, P. Org.
Lett. 2008, 10, 4705−4707. For metalation using carboxylates as
directors see: (b) Nguyen, T.-H.; Castanet, A.-S.; Mortier, J. Org. Lett.
Chem. 2004, 69, 2362−2366.
For a Ni-catalyzed Negishi cross-
coupling with 2.5 equiv sec-butyl-zinc bromide or isopropyl-zinc
bromide and 4-bromophenol, see: (d) Joshi-Pangu, A.; Ganesh, M.;
Biscoe, M. R. Org. Lett. 2011, 13, 1218−1221.
(35) For a palladium-catalyzed Negishi coupling with 4-bromophenol
protected as the tert-butyldimethylsilyl derivative, see: (a) Johnson, A.
T.; Wang, L.; Gillett, S. J.; Chandraratna, R. A. S. Bioorg. Med. Chem.
Lett. 1999, 9, 573−576. The organozinc reagent of 4-bromophenol
has been previously made by cobalt catalysis in 6% corrected GC yield
along with 94% phenol: (b) Fillon, H.; Gosmini, C.; Per
Chem. Soc. 2003, 125, 3867−3870.
́
ichon, J. J. Am.
(36) (a) Manolikakes, G.; Schade, M. A.; Hernandez, C. M. o.; Mayr,
H.; Knochel, P. Org. Lett. 2008, 10, 2765−2768. (b) Sase, S.; Jaric, M.;
Metzger, A.; Malakhov, V.; Knochel, P. J. Org. Chem. 2008, 73, 7380−
7382.
(37) Bordwell, F. G. Acc. Chem. Res. 1988, 21, 456−463.
(38) The pKa of PhSO2NHPh as been reported to be 11.9 in DMSO:
Cheng, J.-P.; Zhao, Y. Tetrahedron 1993, 49, 5267−5276.
(39) The pKa of benzoic acid is reported to be 11.0. Inductive effects
should make 4-bromobenzoic acid more acidic. Olmstead, W. N.;
Bordwell, F. G. J. Org. Chem. 1980, 45, 3299−3305.
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