Journal of the American Chemical Society
Page 4 of 8
(19) Osakada, K.; Yamamoto, T., Coord. Chem. Rev. 2000, 198, 379.
Supporting Information. Supplementary Figures S1-S13, full experi-
mental details, and characterization data for all new compounds are
available in the Supporting Information. This material is available free
(20) Yamamoto, T.; Kohara, T.; Yamamoto, A., Bull. Chem. Soc. Jpn.
1981, 54, 2010.
1
2
3
4
5
6
7
8
(21) We have observed that iodoocumene (1b) can be formed in 65%
yield from the reaction of (L)NiII(2-cumyl)I (7) with iodobenzene (1a).
This apparent reversibility complicates analysis. See Figure S4 in
Supporting Information.
(22) (a) Uchino, M.; Yamamoto, A.; Ikeda, S., J. Organomet. Chem.
1970, 24, C63; (b) Kim, Y.-J.; Sato, R.; Maruyama, T.; Osakada, K.;
Yamamoto, T., Dalton Trans. 1994, 943.
AUTHOR INFORMATION
Corresponding Author
* daniel.weix@rochester.edu
(23) (a) Yamamoto, T.; Kohara, T.; Osakada, K.; Yamamoto, A., Bull.
Chem. Soc. Jpn. 1983, 56, 2147; (b) Anderson, T. J.; Jones, G. D.; Vicic, D.
A., J. Am. Chem. Soc. 2004, 126, 8100; (c) Jones, G. D.; Martin, J.;
McFarland, C.; Allen, O.; Hall, R.; Haley, A.; Brandon, R.; Konovalova, T.;
Desrochers, P.; Pulay, P.; Vicic, D., J. Am. Chem. Soc. 2006, 128, 13175; (d)
Csok, Z.; Vechorkin, O.; Harkins, S. B.; Scopelliti, R.; Hu, X., J. Am. Chem.
Soc. 2008, 130, 8156.
ACKNOWLEDGMENT
9
This work is funded by the NIH (R01 GM097243). Analytical data
were obtained from the CENTC Elemental Analysis Facility at the
University of Rochester, funded by NSF CHE-0650456. We thank W.
W. Brennessel (Univ. of Rochester) for determination of the X-Ray
structures of 7 and 8; S. C. M. Dorn (Univ. of Rochester) for spectro-
scopic assistance; P. T. Wolczanski (Cornell Univ.) for suggesting a
radical chain mechanism; R. G. Bergman (Univ. of California, Berke-
ley) for suggesting the experiment in Figure 4; L. K. G. Ackerman, D.
A. Everson, P. L. Holland, W. D. Jones (Univ. of Rochester), and J. F.
Hartwig (Univ. of California, Berkeley) for helpful discussions.
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
(24) This stoichiometric reactivity was first reported by Ikeda in ref.
22a. The first catalytic, electrochemical example was probably reported in
the thesis of S. Mabrouk, as noted in ref. 13.
(25) In contrast to our results, Yamamoto reported that (dppe)Ni(Me)2
reacted with chlorobenzene to produce toluene in good yield. See ref. 23a.
(26) (a) Klein, H.-F.; Bickelhaupt, A.; Jung, T.; Cordier, G.,
Organometallics 1994, 13, 2557; (b) Dimitrov, V.; Linden, A., Angew.
Chem., Int. Ed. 2003, 42, 2631; (c) Klein, H.-F.; Kraikivskii, P., Angew.
Chem., Int. Ed. 2009, 48, 260.
REFERENCES
(1) (a) Miyaura, N.; Yamada, K.; Suzuki, A., Tetrahedron Lett. 1979, 20,
3437; (b) Miyaura, N.; Suzuki, A., Chem. Rev. 1995, 95, 2457; (c) Suzuki,
A., Angew. Chem., Int. Ed. 2011, 50, 6722.
(27) (a) Phapale, V. B.; Buñuel, E.; García-Iglesias, M.; Cárdenas, D. J.,
Angew. Chem., Int. Ed. 2007, 46, 8790; (b) Vechorkin, O.; Proust, V.; Hu,
X., J. Am. Chem. Soc. 2009, 131, 9756; (c) Kinney, R. J.; Jones, W. D.;
Bergman, R. G., J. Am. Chem. Soc. 1978, 100, 7902; (d) Ash, C. E.; Hurd, P.
W.; Darensbourg, M. Y.; Newcomb, M., J. Am. Chem. Soc. 1987, 109, 3313;
(e) Péralez, E.; Négrel, J.-C.; Chanon, M., Tetrahedron 1995, 51, 12601.
(28) Terao, J.; Watanabe, H.; Ikumi, A.; Kuniyasu, H.; Kambe, N., J. Am.
Chem. Soc. 2002, 124, 4222.
(2) (a) Carey, J.; Laffan, D.; Thomson, C.; Williams, M., Org. Biomol.
Chem. 2006, 4, 2337; (b) Magano, J.; Dunetz, J. R., Chem. Rev. 2011, 111,
2177; (c) Roughley, S. D.; Jordan, A. M., J. Med. Chem. 2011, 54, 3451.
(3) From survey of commercial availability on SciFinder Scholar (CAS)
of RBX2, RZnX, RI, and RBr.
(4) (a) Knochel, P., Handbook of functionalized organometallics :
applications in synthesis. Wiley-VCH: Weinheim, 2005; p 653; (b) Mkhalid,
I. A. I.; Barnard, J. H.; Marder, T. B.; Murphy, J. M.; Hartwig, J. F., Chem.
Rev. 2009, 110, 890; (c) Molander, G. A.; Trice, S. L. J.; Kennedy, S. M.;
Dreher, S. D.; Tudge, M. T., J. Am. Chem. Soc. 2012, 134, 11667; (d)
Robbins, D. W.; Hartwig, J. F., Angew. Chem., Int. Ed. 2012, 52, 933.
(5) (a) Hassan, J.; Sévignon, M.; Gozzi, C.; Schulz, E.; Lemaire, M.,
Chem. Rev. 2002, 102, 1359; (b) Alberico, D.; Scott, M. E.; Lautens, M.,
Chem. Rev. 2007, 107, 174; (c) Ackermann, L.; Vicente, R.; Kapdi, A. R.,
Angew. Chem., Int. Ed. 2009, 48, 9792; (d) Lyons, T. W.; Sanford, M. S.,
Chem. Rev. 2010, 110, 1147; (e) Vechorkin, O.; Proust, V.; Hu, X., Angew.
Chem., Int. Ed. 2010, 49, 3061; (f) Yamaguchi, J.; Yamaguchi, A. D.; Itami,
K., Angew. Chem., Int. Ed. 2012, 51, 8960.
(29) The addition of a small amount (0.2 mol %) of BHT slowed down
the reaction rate, but attempts to trap the alkyl radical intermolecularly
have not yet provided conclusive results.
(30) Newcomb, M., Kinetics of Radical Reactions: Radical Clocks. In
Radicals in Organic Synthesis, 1st ed.; Renaud, P.; Sibi, M. P., Eds. Wiley-
VCH: Weinheim, 2001; Vol. 1, pp 317-336.
(31) Although 2b has been applied to many transition-metal-catalyzed
reactions, non-radical rearrangement of cyclopropylmethylnickel
intermediates is known. See the following endnote.
(32) (a) Pinke, P. A.; Stauffer, R. D.; Miller, R. G., J. Am. Chem. Soc.
1974, 96, 4229; (b) Masarwa, A.; Marek, I., Chem.–Eur. J. 2010, 16, 9712;
(c) Nakamura, I.; Yamamoto, Y., Adv. Synth. Catal. 2002, 344, 111.
(33) Bradley, J. S.; Connor, D. E.; Dolphin, D.; Labinger, J. A.; Osborn,
J. A., J. Am. Chem. Soc. 1972, 94, 4043.
(6) Everson, D. A.; Shrestha, R.; Weix, D. J., J. Am. Chem. Soc. 2010,
132, 920.
(34) A reviewer suggested, correctly, that a radical-chain oxidative
addition to form (L)NiIV(Ar)(Alkyl)X2 would also be consistent with our
results. While we cannot rule out this possibility, it would require that
reductive elimination from (L)NiIII(Ar)(Alkyl)X be slower than its
reaction with alkyl-X. Decomposition of diorganonickel(III) complexes is
reported to be rapid, see the following endnote.
(35) (a) Zhang, C.-P.; Wang, H.; Klein, A.; Biewer, C.; Stirnat, K.;
Yamaguchi, Y.; Xu, L.; Gomez-Benitez, V.; Vicic, D. A., J. Am. Chem. Soc.
2013, 135, 8141; (b) Alonso, P. J.; Arauzo, A. B.; García-Monforte, M. A.;
Martín, A.; Menjón, B.; Rillo, C.; Tomás, M., Chem.–Eur. J. 2009, 15,
11020.
(36) Two pieces of evidence argue that arylnickel(II) is the resting state
of the catalyst: (1) reaction mixtures are red, consistent with the presence
of arylnickel(II), but not (L)Ni0 (purple) or (L)NiIII2 (light green); (2)
acid-quenched aliquots of the reaction in Scheme 1 showed the presence of
arene (48% of the catalyst loading) during periods of product formation,
but not at the end of the reaction (8% of catalyst loading), consistent with
an arylnickel intermediate being present during the reaction, but not at the
end of the reaction. See Figure S7 in the Supporting Information.
(37) Breitenfeld, J.; Ruiz, J.; Wodrich, M. D.; Hu, X., J. Am. Chem. Soc.
2013, 135, 12004.
(38) Yakhvarov, D. G.; Budnikova, Y. H.; Sinyashin, O. G., Russ. Chem.
Bull. 2003, 52, 567.
(39) van de Kuil, L. A.; Grove, D. M.; Gossage, R. A.; Zwikker, J. W.;
Jenneskens, L. W.; Drenth, W.; van Koten, G., Organometallics 1997, 16,
4985.
(40) (a) Grove, D. M.; Van Koten, G.; Zoet, R.; Murrall, N. W.; Welch,
A. J., J. Am. Chem. Soc. 1983, 105, 1379; (b) Higgs, A. T.; Zinn, P. J.;
Simmons, S. J.; Sanford, M. S., Organometallics 2009, 28, 6142.
(41) (a) Jahn, U., Top. Curr. Chem. 2012, 320, 121; (b) Jahn, U., Top.
Curr. Chem. 2012, 320, 191; (c) Jahn, U., Top. Curr. Chem. 2012, 320, 323.
(42) For radical intermediates in Pd-catalyzed coupling, see:
Manolikakes, G.; Knochel, P., Angew. Chem., Int. Ed. 2009, 48, 205-209.
(7) Everson, D. A.; Jones, B. A.; Weix, D. J., J. Am. Chem. Soc. 2012, 134,
6146.
(8) (a) Durandetti, M.; Nédélec, J.-Y.; Périchon, J., J. Org. Chem. 1996,
61, 1748; (b) Amatore, M.; Gosmini, C., Chem.--Euro. J. 2010, 16, 5848;
(c) Yan, C.-S.; Peng, Y.; Xu, X.-B.; Wang, Y.-W., Chem.–Eur. J. 2012, 18,
6039; (d) Wang, S.; Qian, Q.; Gong, H., Org. Lett. 2012, 14, 3352.
(9) (a) Wotal, A. C.; Weix, D. J., Org. Lett. 2012, 14, 1476; (b) Wu, F.;
Lu, W.; Qian, Q.; Ren, Q.; Gong, H., Org. Lett. 2012, 14, 3044; (c) Yin, H.;
Zhao, C.; You, H.; Lin, K.; Gong, H., Chem. Commun. 2012, 48, 7034.
(10) (a) Shrestha, R.; Weix, D. J., Org. Lett. 2011, 13, 2766; (b)
Shrestha, R.; Dorn, S. C. M.; Weix, D. J., J. Am. Chem. Soc. 2013, 135, 751.
(11) (a) Hegedus, L. S.; Miller, L. L., J. Am. Chem. Soc. 1975, 97, 459;
(b) Hegedus, L. S.; Thompson, D. H. P., J. Am. Chem. Soc. 1985, 107, 5663.
(12) (a) Tsou, T.; Kochi, J., J. Am. Chem. Soc. 1979, 101, 7547; (b)
Troupel, M.; Rollin, Y.; Sibille, S.; Périchon, J.; Fauvarque, J.-F., J.
Organomet. Chem. 1980, 202, 435; (c) Colon, I.; Kelsey, D. R., J. Org.
Chem. 1986, 51, 2627; (d) Amatore, C.; Jutand, A., Organometallics 1988,
7, 2203.
(13) (a) Folest, J. C.; Périchon, J.; Fauvarque, J. F.; Jutand, A., J.
Organomet. Chem. 1988, 342, 259; (b) Durandetti, M.; Devaud, M.;
Périchon, J., New J. Chem. 1996, 20, 659.
(14) (a) Amatore, M.; Gosmini, C., Chem. Commun. 2008, 5019; (b)
Czaplik, W. M.; Mayer, M.; Jacobi von Wangelin, A., Angew. Chem., Int. Ed.
2009, 48, 607; (c) Krasovskiy, A.; Duplais, C.; Lipshutz, B., J. Am. Chem.
Soc. 2009, 131, 15592.
(15) Yamamoto, T.; Wakabayashi, S.; Osakada, K., J. Organomet. Chem.
1992, 428, 223.
(16) Yakhvarov, D.; Budnikova, Y.; Sinyashin, O., Russ. J. Electrochem.
2003, 39, 1261.
(17) See Supporting Information for details.
(18) Kuroboshi, M.; Tanaka, M.; Kishimoto, S.; Goto, K.; Mochizuki,
M.; Tanaka, H., Tetrahedron Lett. 2000, 41, 81.
ACS Paragon Plus Environment