A R T I C L E S
Engle et al.
Scheme 1. Versatile Reactivity of [Pd(II)-R] Intermediates
catalysis remain underdeveloped. The principal driving force
that has propelled Pd(0)-catalyzed coupling chemistry during
the past several decades has been the development of bulky
phosphine and N-heterocyclic carbene (NHC) ligands that
promote both the oxidative addition and reductive elimination
steps, thereby improving the reaction rate, lowering the requisite
catalyst loading, and expanding the substrate scope.41 The
advancements in ligand design have resulted in truly practical
(24) For domino reactions involving C-H activation/C-C bond formation
along a Pd(0)/Pd(II)/Pd(IV) catalytic cycle, see: (a) Catellani, M.;
Frignani, F.; Rangoni, A. Angew. Chem., Int. Ed. 1997, 36, 119. (b)
Mauleo´n, P.; Alonso, I.; Carretero, J. C. Angew Chem., Int. Ed. 2001,
40, 1291. For recent developments using Pd(0)/Pd(II)/Pd(IV) catalysis,
see: (c) Mariampillai, B.; Alliot, J.; Li, M.; Lautens, M. J. Am. Chem.
Soc. 2007, 129, 15372. (d) Gericke, K. M.; Chai, D. I.; Bieler, N.;
Lautens, M. Angew. Chem., Int. Ed. 2009, 48, 1447.
(25) For C-H arylation reactions using Pd(II)/(IV) catalysis, see: (a) Xia,
M.; Chen, Z. C. Synth. Commun. 2000, 30, 531. (b) Kalyani, D.;
Deprez, N. R.; Desai, L. V.; Sanford, M. S. J. Am. Chem. Soc. 2005,
127, 7330. (c) Daugulis, O.; Zaitsev, V. G. Angew. Chem., Int. Ed.
2005, 44, 4046. (d) Zaitsev, V. G.; Shabashov, D.; Daugulis, O. J. Am.
Chem. Soc. 2005, 127, 13154. (e) Deprez, N. R.; Kalyani, D.; Krause,
A.; Sanford, M. S. J. Am. Chem. Soc. 2006, 128, 4972. (f) Reddy,
B. V. S.; Reddy, L. R.; Corey, E. J. Org. Lett. 2006, 8, 3391. (g)
Lazareva, A.; Daugulis, O. Org. Lett. 2006, 8, 5211. (h) Shabashov,
D.; Daugulis, O. J. Am. Chem. Soc. 2010, 132, 3965.
and others20-29 have demonstrated several catalytic reactions
in which [Pd(II)-R] intermediates generated by C-H activation
react with strong oxidants to induce reductive elimination from
high-energy Pd(III)30,31 or Pd(IV)32 species. Despite our early
success in this direction, the bulk of our efforts have centered
on developing novel carbon-carbon and carbon-heteroatom
bond-forming reactions via a Pd(II)/Pd(0) catalytic cycle. This
strategy has proven to be a remarkably fruitful research area,
as many of the reactions depicted in Scheme 1 have already
been demonstrated.33-40
(26) For C-H fluorination using Pd(II)/(IV) catalysis, see: (a) Hull, K. L.;
Anani, W. Q.; Sanford, M. S. J. Am. Chem. Soc. 2006, 128, 7134.
(27) For C-H halogenation using Pd(II)/(IV) catalysis, see: Kalyani, D.;
Dick, A. R.; Anani, W. Q.; Sanford, M. S. Org. Lett. 2006, 8, 2523.
(28) For C-H amination using Pd(II)/(IV) catalysis, see: (a) Jordan-Hore,
J. A.; Johansson, C. C. C.; Gulias, M.; Beck, E. M.; Gaunt, M. J.
J. Am. Chem. Soc. 2008, 130, 16184. For Pd-catalyzed C–H amination
using nitrene insertion, see: (b) Thu, H.-Y.; Yu, W.-Y.; Che, C.-M.
J. Am. Chem. Soc. 2006, 128, 9048.
(29) For C-H sulfonylation using Pd(II)/(IV) catalysis, see: Zhao, X.;
Dimitrijevic´, E.; Dong, V. M. J. Am. Chem. Soc. 2009, 131, 3466.
(30) For evidence and discussion of Pd(III) intermediates in C-H activation
reactions, see: (a) Powers, D. C.; Ritter, T. Nat. Chem. 2009, 1, 302.
(b) Powers, D. C.; Geibel, M. A. L.; Klein, J. E. M. N.; Ritter, T.
J. Am. Chem. Soc. 2009, 131, 17050. (c) Deprez, N. R.; Sanford, M. S.
J. Am. Chem. Soc. 2009, 131, 11234. For pioneering inorganic studies
of Pd(III) species, see: (d) Cotton, F. A.; Koshevoy, I. O.; Lahuerta,
P.; Murillo, C. A.; Sanau´, M.; Ubeda, M. A.; Zhao, Q. J. Am. Chem.
Soc. 2006, 128, 13674. For a related study concerning Pt(III)
intermediates, see: (e) Whitfield, S. R.; Sanford, M. S. Organometallic
2008, 27, 1683. For a recent inorganic study, see: (f) Khusnutdinova,
J. R.; Rath, N. P.; Mirica, L. M. J. Am. Chem. Soc. 2010, 132, 7303.
(31) For an example of C-H amination where Pd(III) is implicated in the
catalytic cycle, see: Mei, T.-S.; Wang, X.; Yu, J.-Q. J. Am. Chem.
Soc. 2009, 131, 10806.
In comparison to the state of the art in traditional Pd(0)
coupling chemistry, C-H activation reactions using Pd(II)/Pd(0)
(14) For reviews of Pd-catalyzed C-H activation reactions, see: (a) Jia,
C.; Kitamura, T.; Fujiwara, Y. Acc. Chem. Res. 2001, 34, 633. (b)
Satoh, T.; Miura, M. Chem. Lett. 2007, 36, 200. (c) Seregin, I. V.;
Gevorgyan, V. Chem. Soc. ReV. 2007, 36, 1173. (d) Campeau, L.-C.;
Stuart, D. R.; Fagnou, K. Aldrichimica Acta 2007, 40, 35. (e) Alberico,
D.; Scott, M. E.; Lautens, M. Chem. ReV. 2007, 107, 174. (f) Li, B.-
J.; Yang, S.-D.; Shi, Z.-J. Synlett 2008, 949. (g) Kakiuchi, F.; Kochi,
T. Synthesis 2008, 3013. (h) Daugulis, O.; Do, H.-Q.; Shabashov, D.
Acc. Chem. Res. 2009, 42, 1074. (i) Chen, X.; Engle, K. M.; Wang,
D.-H.; Yu, J.-Q. Angew. Chem., Int. Ed. 2009, 48, 5094. (j)
Ackermann, L.; Vicente, R.; Kapdi, A. R. Angew. Chem., Int. Ed.
2009, 48, 9792. (k) Lyons, T. W.; Sanford, M. S. Chem. ReV. 2010,
110, 1147.
(15) For diastereoselective C-H iodination and acetoxylation using Pd(II)/
Pd(IV) catalysis from our group, see: (a) Giri, R.; Chen, X.; Yu, J.-Q.
Angew. Chem., Int. Ed. 2005, 44, 2112. (b) Giri, R.; Liang, J.; Lei,
J.-G.; Li, J.-J.; Wang, D.-H.; Chen, X.; Naggar, I. C.; Guo, C.; Foxman,
B. M.; Yu, J.-Q. Angew. Chem., Int. Ed. 2005, 44, 7420.
(16) For C-H halogenation using Pd(II)/Pd(IV) catalysis from our group,
see: (a) Mei, T.-S.; Giri, R.; Maugel, N.; Yu, J.-Q. Angew. Chem.,
Int. Ed. 2008, 47, 5215.
(32) For reviews of organopalladium(IV) chemistry, see: (a) Yu, J.-Q.; Giri,
R.; Chen, X. Org. Biomol. Chem. 2006, 4, 4041. (b) Mun˜iz, K. Angew.
Chem., Int. Ed. 2009, 121, 9576. (c) Xu, L.-M.; Li, B.-J.; Yang, Z.;
Shi, Z.-J. Chem. Soc. ReV. 2010, 39, 712. (d) Sehnal, P.; Taylor,
R. J. K.; Fairlamb, I. J. S. Chem. ReV. 2010, 110, 824.
(17) For C-H fluorination using Pd(II)/Pd(IV) catalysis from our group,
see: Wang, X.; Mei, T.-S.; Yu, J.-Q. J. Am. Chem. Soc. 2009, 131,
7520.
(33) For the initial reports of Pd(II)-mediated arene C-H olefination, see:
(a) Moritani, I.; Fujiwara, Y. Tetrahedron Lett. 1967, 8, 1119. (b)
Fujiwara, Y.; Moritani, I.; Matsuda, M.; Teranishi, S. Tetrahedron
Lett. 1968, 9, 633.
(18) For C-H amination using Pd(II)/Pd(IV) catalysis from our group, see:
Wasa, M.; Yu, J.-Q. J. Am. Chem. Soc. 2008, 130, 14058.
(19) For an example of C-H alkylation using Pd(II)/Pd(IV) catalysis from
our group, see: Zhang, Y.-H.; Shi, B.-F.; Yu, J.-Q. Angew. Chem.,
Int. Ed. 2009, 48, 6097.
(34) For selected examples of subsequent work to improve the catalytic
turnover and expand the substrate scope of Pd(II)-mediated C-H
olefination, see: (a) Fujiwara, Y.; Moritani, I.; Danno, S.; Asano, R.;
Teranishi, S. J. Am. Chem. Soc. 1969, 91, 7166. (b) Asano, R.;
Moritani, I.; Fujiwara, Y.; Teranishi, S. J. Chem. Soc. D: Chem.
Commun. 1970, 1293. (c) Fujiwara, Y.; Asano, R.; Moritani, I.;
Teranishi, S. J. Org. Chem. 1976, 41, 1681. (d) Tsuji, J.; Nagashima,
H. Tetrahedron 1984, 40, 2699. (e) Jia, C.; Lu, W.; Kitamura, T.;
Fujiwara, Y. Org. Lett. 1999, 1, 2097. (f) Jia, C.; Piao, D.; Oyamada,
J.; Lu, W.; Kitamura, T.; Fujiwara, Y. Science 2000, 287, 1992. (g)
Yokota, T.; Tani, M.; Sakaguchi, S.; Ishii, Y. J. Am. Chem. Soc. 2003,
125, 1476.
(20) For early reports of C-H iodination using Pd(II)/(IV) catalysis, see:
(a) Fahey, D. R. J. Organomet. Chem. 1971, 27, 283. (b) Andrienko,
O. S.; Goncharov, V. S.; Raida, V. S. Russ. J. Org. Chem. 1996, 32,
79.
(21) For early reports of C-H acetoxylation using Pd(II)/(IV) catalysis,
see: (a) Henry, P. M. J. Org. Chem. 1971, 36, 1886. (b) Yoneyama,
T.; Crabtree, R. H. J. Mol. Catal. A: Chem. 1996, 108, 35.
(22) For C-H acetoxylation using Pd(II)/(IV) catalysis, see: (a) Dick, A. R.;
Hull, K. L.; Sanford, M. S. J. Am. Chem. Soc. 2004, 126, 2300. (b)
Desai, L. V.; Hull, K. L.; Sanford, M. S. J. Am. Chem. Soc. 2004,
126, 9542.
(35) For an example of Pd(II)-catalyzed C-H olefination using haloolefins,
see: Zaitsev, V. G.; Daugulis, O. J. Am. Chem. Soc. 2005, 127, 4156.
(36) For C-H amination using Pd(II)/Pd(0) catalysis, see: (a) Tsang,
W. C. P.; Zheng, N.; Buchwald, S. L. J. Am. Chem. Soc. 2005, 127,
14560. (b) Inamoto, K.; Saito, T.; Katsuno, M.; Sakamoto, T.; Hiroya,
K. Org. Lett. 2007, 9, 2931.
(23) For early reports of C-H alkylation using Pd(II)/Pd(IV) catalysis, see:
(a) Tremont, S. J.; Rahman, H. U. J. Am. Chem. Soc. 1984, 106, 5759.
(b) McCallum, J. S.; Gasdaska, J. R.; Liebeskind, L. S.; Tremont, S. J.
Tetrahedron Lett. 1989, 30, 4085.
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