ChemComm
DOI: 10.1039/C4CC09576F
The calculated distances between the palladium atom and the Cꢀ
H σ bond were 1.95 Å in TS (AꢀB) and 2.01 Å in TS (AꢀB’),
respectively, obviously within the distance of a threeꢀcenter twoꢀ
electron agostic interaction. Besides, a lower energy discrepancy
of about 3.0 kcal/mol was observed for TS (AꢀB) over TS (Aꢀ
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12984; (j) W. R. Gutekunst, R. Gianatassio and P. S. Baran, Angew.
Chem., Int. Ed., 2012, 51, 7507; (k) R. Shang, L. Ilies, A. Matsumoto
and E. Nakamura, J. Am. Chem. Soc., 2013, 135, 6030; (l) R. Parella,
B. Gopalakrishnan and S. A. Babu, Org. Lett., 2013, 15, 3238; (m) X.
Wu, Y. Zhao and H. Ge, Chem. Eur. J., 2014, 20, 9530.
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Selected examples on other BDGs: (a) R. K. Rit, M. R. Yadav and A.
K. Sahoo, Org. Lett., 2012, 14, 3724; (b) F.ꢀJ. Chen, S. Zhao, F. Hu,
Q. Zhang, S.ꢀQ. Zhang and B.ꢀF. Shi, Chem. Sci., 2013, 4, 4187; (c)
N. Ghavtadze, F. S. Melkonyan, A. V. Gulevich, C. Huang and V.
Gevorgyan, Nature Chem., 2014, 6, 122; (d) S.ꢀY. Zhang, G. He, W.
A. Nack, Y. Zhao, Q. Li and G. Chen, J. Am. Chem. Soc., 2013, 135,
2124; (e) N. Hasegawa, V. Charra, S. Inoue, Y. Fukumoto and N.
Chatani, J. Am. Chem. Soc., 2011, 133, 8070; (f) W. R. Gutekunst
and P. S. Baran, J. Am. Chem. Soc., 2011, 133, 19076; (g) E. T.
Nadres and O. Daugulis, J. Am. Chem. Soc., 2012, 134, 7; (h) N.
Rodríguez, J. A. RomeroꢀRevilla, M. A. FernándezꢀIbáñez and J. C.
Carretero, Chem. Sci., 2013, 4, 175; (i) X. Ye, Z. He, T. Ahmed, K.
Weise, N. G. Akhmedov, J. L. Petersen and X. Shi, Chem. Sci., 2013,
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B’), suggesting a favorable αꢀselectivity in this C(sp )ꢀH bond
activation, which was in agreement with our experiment results.
Further investigation on the geometry of the optimized
intermediate A revealed that the 5,6ꢀfused palladacycle is difficult
to be formed as it requires a significant rotation of the C(O)ꢀC(α)
bond, which increases molecular energy apparently (See ESI).
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Conclusions
In conclusion, we have successfully developed a novel removable
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bidentate directing group (BDG)ꢀcontrolled αꢀC(sp )ꢀH
4
, 3712. (j) R. K. Rit, M. R. Yadav, K. Ghosh, M. Shankar, and A. K.
15
acetoxylation via
a
unique [4,6]ꢀbicyclic cyclopalladation
Sahoo, Org. Lett., 2014, 16, 5258.
S. Li, G. Chen, C.ꢀG. Feng, W. Gong and J.ꢀQ. Yu, J. Am. Chem.
Soc., 2014, 136, 5267.
Selected reviews on transition metalꢀcatalyzed αꢀarylation of
carbonyl compounds: (a) C. C. C. Johansson and T. J. Colacot,
Angew. Chem., Int. Ed., 2010, 49, 676; (b) F. Bellina and R. Rossi,
Chem. Rev., 2010, 110, 1082.
Transition metalꢀcatalyzed αꢀalkylation of carbonyl compounds: F.
Mo and G. Dong, Science, 2014, 345, 68.
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pathway. This is the first example of αꢀC(sp )ꢀH
oxidation/acetoxylation of amides through a Pdꢀcatalyzed BDGꢀ
induced CꢀH activation process. The cheap and ample
commercial source of the newly discovered BDG, together with
its easy onꢀandꢀoff property, makes this reaction with great
practical utility.
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Selected reviews on αꢀoxidation of amides: (a) S. V. Ley, T. D.
Sheppard, R. M. Myers and M. S. Chorghade, Bull. Chem. Soc. Jpn.,
2007, 80, 1451; (b) T. Vilaivan and W. Bhanthumnavin, Molecules,
Acknowledgment
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This work is supported by Chinese National Natural
Science Foundation (81430080, 81125021, 81373277) and
by the Major State Basic Research Development Program
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010, 15, 917; (c) F. A. Davis and B.ꢀC. Chen, Chem. Rev., 1992,
92, 919.
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10 Selected examples on Pdꢀcatalyzed C(sp )ꢀH oxidation: (a) G. Shan,
X. Yang, Y. Zong and Y. Rao, Angew. Chem., Int. Ed., 2013, 52,
13606; (b) G. He, Y. Zhao, S. Zhang, C. Lu and G. Chen, J. Am.
Chem. Soc., 2012, 134, 3; (c) S.ꢀY. Zhang, G. He, Y. Zhao, K.
Wright, W. A. Nack and G. Chen, J. Am. Chem. Soc., 2012, 134,
7313; d) T. Cheng, W. Yin, Y. Zhang, Y. Zhang and Y. Huang, Org.
Biomol. Chem., 2014, 12, 1405; (e) A. R. Dick, K. L. Hull and M. S.
Sanford, J. Am. Chem. Soc., 2004, 126, 2300; (f) L. V. Desai, K. L.
Hull and M. S. Sanford, J. Am. Chem. Soc., 2004, 126, 9542; (g) S.
R. Neufeldt and M. S. Sanford, Org. Lett., 2010, 12, 532; (h) K. J.
Stowers, A. Kubota and M. S. Sanford, Chem. Sci., 2012, 3, 3192; (i)
R. Giri, J. Liang, J.ꢀG. Lei, J.ꢀJ. Li, D.ꢀH. Wang, X. Chen, I. C.
Naggar, C. Guo, B. M. Foxman and J.ꢀQ. Yu, Angew. Chem., Int.
Ed., 2005, 44, 7420; (j) D.ꢀH. Wang, X.ꢀS. Hao, D.ꢀF. Wu and J.ꢀQ.
Yu, Org. Lett., 2006, 8, 3387; (k) Z. Ren, F. Mo and G. Dong, J. Am.
Chem. Soc., 2012, 134, 16991; (l) L. Zhou and W. Lu, Org. Lett.,
(
2015CB910603).
Notes and references
a
CAS Key Laboratory of Receptor Research, and Synthetic Organic &
Medicinal Chemistry Laboratory (SOMCL), Shanghai Institute of Materia
Medica (SIMM), Chinese Academy of Sciences, Shanghai 201203, China.
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b
Drug Discovery and Design Center, Shanghai Institute of Materia
Medica (SIMM), Chinese Academy of Sciences, Shanghai 201203, China.
c
Department of Radiology, School of Medicine, Stanford University,
Stanford, California, 94305-5484.
† Electronic Supplementary Information (ESI) available: See
DOI: 10.1039/b000000x/
‡
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These two authors contributed equally to this work.
Selected reviews on directed CꢀH activations: (a) Y. J. Park and C.ꢀ
H. Jun, Bull. Korean Chem. Soc., 2005, 26, 871; (b) T. M. Lyons and
M. S. Sanford, Chem. Rev., 2010, 110, 1147; (c) K. M. Engle, T.ꢀS.
Mei, M. Wasa and J.ꢀQ. Yu, Acc. Chem. Res., 2012, 45, 788; (d) D.
A. Colby, A. S. Tsai, R. G. Bergman and J. A. Ellman, Acc. Chem.
Res., 2012, 45, 814.
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014, 16, 508.
10 11 A. McNally, B. Haffemayer, B. S. L. Collons and M. J. Gaunt,
Nature, 2014, 510, 129.
For computational details and references, see the Supporting
Information.
(a) M. Lafrance, S. I. Gorelsky and K. Fagnou, J. Am. Chem. Soc.,
2007, 129, 14570; (b) S. Rousseaux, M. Davi, J. SofackꢀKreutzer, C.
Pierre, C. E. Kefalidis, E. Clot and K. Fagnou, J. Am. Chem. Soc.,
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Selected reviews of C(sp )ꢀH functionalization: (a) R. Jazzar, J.
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Hitce, A. Renaudat, J. SofackꢀKreutaer and O. Baudoin, Chem.-Eur.
J., 2010, 16, 2654; (b) O. Baudoin, Chem. Soc. Rev., 2011, 40, 4902.
Selected review on BDGs: G. Rouquet and N. Chatani, Angew.
Chem., Int. Ed., 2013, 52, 11726.
Selected examples on 8ꢀaminoquinoline as BDGs: (a) M. Corbet and
F. D. Campo, Angew. Chem., Int. Ed., 2013, 52, 9896; (b) V. G.
Zaitsev, D. Shabashov and O. Daugulis, J. Am. Chem. Soc., 2005,
2
010, 132, 10706.
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27, 13154; (c) D. Shabashov and O. Daugulis, J. Am. Chem. Soc.,
010, 132, 3965; (d) L. D. Tran and O. Daugulis, Angew. Chem., Int.
Ed., 2012, 51, 5188; (e) B. V. S. Reddy, L. R. Reddy and E. J. Corey,
Org. Lett., 2006, 8, 3391; (f) Y. Feng, Y. Wang, B. Landgraf, S. Liu
and G. Chen, Org. Lett., 2010, 12, 3414; (g) Y. Feng and G. Chen,
Angew. Chem., Int. Ed., 2010, 49, 958; (h) S. Zhang, Q. Li, G. He,
W. A. Nack and G. Chen, J. Am. Chem. Soc., 2013, 135, 12135; (i)
Y. Ano, M. Tobisu and N. Chatani, J. Am. Chem. Soc., 2011, 133,
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