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DOI: 10.1039/C5CC07455J
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two operating catalytic cycles can be proposed based on the results
described above and the available literature: a facile double chain-
walking isomerization mechanism (Scheme 4, cycle A) and a rather
slow C-H functionalization mechanism (Scheme 4, cycle B). In cycle
A, 2a is isomerized via a formal 1,3-hydride shift through an η3-allyl
Ni hydride intermediate 11 to afford the more thermodynamically
stable 12. In the slow catalytic cycle B, the C-H functionalization
process most likely proceeds through the following steps: (1)
oxidative addition of the C-H bond to afford the Ni-H species, (2)
migratory insertion of 12 into the Ni-H to give 16, and (3) reductive
elimination of 16 to afford 4aa. However, the rate-determining step
is most likely the π-coordination of pyridine onto the metal prior to
the C-H bond cleavage or reductive elimination step.
Notes and references
1
(a) A. R. Katritzky, C. A. Ramsden, E. F. V. Scriven and R. J. K.
Taylor Eds. Comprehensive Heterocyclic Chemistry; Elsevier:
Oxford, 2008, 7; (b) G. D. Henry, Tetrahedron, 2004, 60,
6043; (c) J. P. Michael, Nat. Prod. Rep., 2005, 22, 627 (c) J. S.
Carey, D. Laffan, C. Thomson and M. T. Williams, Org.
Biomol. Chem., 2006, 4, 2337; (d) M. Schlosser and F.
Mongin, Chem. Soc. Rev., 2007, 36, 1161; (e) C. G. Arena and
G. Arico, Curr. Org. Chem., 2010, 14, 546; (f) D. Zhao, J. You
and C. Hu, Chem.– Eur. J., 2011, 17, 5466; (g) J. A. Bull, J. J.
Mousseau, G. Pelletier, and A. B. Charette, Chem. Rev. 2012,
112, 2642.
2
Recent review for CH activation: (a) G. Rouquet and N.
Chatani, Angew. Chem. Int. Ed., 2013, 52, 11726; (b) N. Kuhl,
N. Schröder, and F. Glorius, Adv. Synth. Catal., 2014, 356
,
1443; (c) I. Hussain and T. Singh, Adv. Synth. Catal., 2014,
356, 1661; (d) Q. Liu, R. Jackstell, and M. Beller, Angew.
Chem. Int. Ed., 2013, 52, 13871; (e) A. S. Borovik, Chem. Soc.
Rev., 2011, 40, 1870; (f) S. A. Girard, T. Knauber, and C.-J. Li,
Angew. Chem. Int. Ed., 2013, 53, 74. (g) L. Ackermann, Acc.
Chem. Res., 2014, 47, 281. (h) J. Li, S. De Sarkar and L.
Ackermann, Top. Organomet. Chem., 2015, DOI:
10.1007/3418_2015_130. (i) D. E. Stephens and O. V.
Scheme 3. The reaction of d5-pyridine with allylbenzenes.
Larionov, Tetrahedron.
10.1016/j.tet.2015.08.034.
ASAP.
DOI:
3
Selected literatures of C2-selective: (a) A. M. Berman, J. C.
Lewis, R. G. Bergman and J. A. Ellman, J. Am. Chem. Soc.,
2008, 130, 14926; (b) J. C. Lewis, R. G. Bergman and J. A.
Ellman, J. Am. Chem. Soc., 2007, 129, 5332; (c) A. M. Berman,
R. G. Bergman and J. A. Ellman, J. Org. Chem., 2010, 75,
7863; (d) B. Liu, Y. Huang, J. Lan, F. Song, and J. You, Chem.
Scheme 4. Proposed mechanism
Sci., 2013, 4, 2163; (e) H. Nagae, H. Tsurugi and K. Mashima,
J. Am. Chem. Soc., 2015, 137, 640; (f) R. F. Jordan and D. F.
Taylor, J. Am. Chem. Soc., 1989, 111, 778; (g) B.-T. Guan and
Z. Hou, J. Am. Chem. Soc. 2011, 133, 18086; (h) H. Kaneko, H.
Nagae, H. Tsurugi and K. Mashima, J. Am. Chem. Soc., 2011,
133, 19626; (i) M. Tobisu, I. Hyodo and N. Chatani, J. Am.
Chem. Soc., 2009, 131, 12070; (j) Y. Nakao, K. S. Kanyiva and
T. Hiyama, J. Am. Chem. Soc., 2008, 130, 2448; (k) D. G.
Johnson, J. M. Lynam, N. S. Mistry, J. M. Slattery, R. J.
Thatcher, and A. C. Whitwood, J. Am. Chem. Soc., 2013, 135
,
2222; (l) M. Murakami and S. Hori, J. Am. Chem. Soc., 2003,
125, 4720–4721; (m) H. Nagae, Y. Shibata, H. Tsurugi, and K.
Mashima, J. Am. Chem. Soc., 2015, 137, 640–643.
4
Recent literatures of C4-selective by Ni catalyst: (a) Y. Nakao,
Y. Yamada, N. Kashihara and T. Hiyama, J. Am. Chem. Soc.,
2010, 132, 13666; (b) C.-C. Tsai, W.-C. Shih, C.-H. Fang, C.-Y.
Conclusions
Li, T.-G. Ong, and G. P. A. Yap, J. Am. Chem. Soc., 2010, 132
11887.
Recent literature of C4-selective: T. Andou, Y. Saga, H.
Komai, S. Matsunaga, and M. Kanai, Angew. Chem. Int. Ed.,
2013, 52, 3213.
Selected literatures of C3-selective: (a) M. Ye, G.-L. Gao, A. J.
F. Edmunds, P. A. Worthington, J. A. Morris and J.-Q. Yu, J.
Am. Chem. Soc., 2011, 133, 19090; (b) M. Ye, G.-L. Gao and
J.-Q. Yu, J. Am. Chem. Soc., 2011, 133, 6964. (c) P. Guo, J. M.
Joo, S. Rakshit and D. Sames, J. Am. Chem. Soc., 2011, 133
16338.
(a) M. Perutz, Mechanisms of Cooperativity and Allosteric
Regulation in Proteins; Cambridge University Press:
Cambridge, U.K., 1990; (b) N. M. Goodey and S. J. Benkovic,
Nat. Chem. Biol. 2008, 4, 474; (c) K. Gunasekaran, B. Ma and
R. Nussinov, Proteins 2004, 57, 433; (c) C. Tsai, A. Del Sol and
R. Nussinov, Mol. BioSyst. 2009, 5, 207.
,
In summary, without installing directing groups on the substrate,
we have disclosed
a
novel regiodivergent C-H bond
5
6
functionalization of pyridines with allylbenzenes. The catalytic
method features a cooperative interaction between Ni and Al to
invoke remote para C-H activation via hydroheteroarylation
towards branched and linear isomers, which is unprecedented.
Ongoing work seeks to gain a detailed mechanistic understanding of
the synergy offered by Ni-Al bimetallic catalysis. Such mechanistic
insights will be crucial for the future development of bimetallic
catalysts.
,
7
8
This work was financially supported by the Ministry of Science &
Technology of Taiwan (MOST-104-2628-M-001-005-MY4 grant) and
Academia Sinica Career Development Award (104-CDA-M08).
W.-C. Lee, C.-H. Wang, Y.-H. Lin, W.-C. Shih, and T.-G. Ong,
Org. Lett., 2013, 15, 5358–5361.
4 | J. Name., 2012, 00, 1-3
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