Organic Letters
Letter
Y.; Li, C.-J. J. Am. Chem. Soc. 2006, 128, 4242. (f) Zhang, Y.; Li, C.-J.
Angew. Chem., Int. Ed. 2006, 45, 1949. (g) Li, Z.; Cao, L.; Li, C.-J. Angew.
Chem., Int. Ed. 2007, 46, 6505. (h) Zhang, Y.; Li, C.-J. Eur. J. Org. Chem.
2007, 2007, 4654. (i) Deng, G.; Zhao, L.; Li, C.-J. Angew. Chem., Int. Ed.
2008, 47, 6278. (j) Zhao, L.; Li, C.-J. Angew. Chem., Int. Ed. 2008, 47,
7075. (k) Deng, G.; Li, C.-J. Org. Lett. 2009, 11, 1171. (l) Guo, X.; Li, C.-
J. Org. Lett. 2011, 13, 4977.
(12) (a) Wu, Z.; Pi, C.; Cui, X.; Bai, J.; Wu, Y. Adv. Synth. Catal. 2013,
355, 1971. (b) Wei, W.-T.; Song, R.-J.; Li, J.-H. Adv. Synth. Catal. 2014,
356, 1703.
(13) For transformations of methylene: Bordwell, F. G.; Bares, J. E.;
Bartmess, J. E.; McCollum, G. J.; Van der Puy, M.; Vanier, N. R.;
Matthews, W. S. J. Org. Chem. 1977, 42, 321. For transformations of the
cyano group: (a) Weiberth, F. J.; Hall, S. S. J. Org. Chem. 1987, 52, 3901.
(b) Trivedi, B. K.; Holmes, H. A.; Stoeber, T. L.; Blankley, C. J.; Roark,
W. H.; Picard, J. A.; Shaw, M. K.; Essenburg, A. D.; Stanfield, R. L.;
Krause, B. R. J. Med. Chem. 1993, 36, 3300. (c) Makosza, M. Chem. Soc.
Rev. 2010, 39, 2855. (d) Velcicky, J.; Soicke, A.; Steiner, R.; Schmalz, H.-
G. J. Am. Chem. Soc. 2011, 133, 6948. (e) Jinzaki, T.; Arakawa, M.;
Kinoshita, H.; Ichikawa, J.; Miura, K. Org. Lett. 2013, 15, 3750. (f) Yi, H.;
Zhang, X.; Qin, C.; Liao, Z.; Liu, J.; Lei, A. Adv. Synth. Catal. 2014, 356,
2873.
Author Contributions
∥H.S. and L.W. contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Financial support from NSFC (21402128, 21502042), Beijing
Natural Science Foundation (2172015, 2144045), Key Labo-
ratory of Bioorganic Phosphorus Chemistry and Chemical
Biology (Ministry of Education), and Capital Normal University
are greatly appreciated. We thank Ziye Cai and Na Li in our
group for reproducing the results of 2a and 2l.
REFERENCES
■
(1) (a) Handbook of C−H Transformations: Applications in Organic
Synthesis; Dyker, G., Ed.; Wiley-VCH: Weinheim, 2005. (b) C−H
Activation; Yu, J.-Q., Shi, Z., Eds.; Springer: Heidelberg, 2010. (c) C−H
Bond Activation in Organic Synthesis; Li, J. J., Ed.; CRC Press: New York,
2015. (d) From C−H to C−C Bonds: Cross-Dehydrogenative Coupling; Li,
C.-J., Ed.; Royal Society of Chemistry: Cambridge, 2015. (e) C−H Bond
Activation and Catalytic Functionalization I and II; Dixneuf, P. H.,
Doucet, H., Eds.; Springer: Berlin, 2016. (f) Sun, C.-L.; Li, B.-J.; Shi, Z.-J.
Chem. Rev. 2011, 111, 1293.
(14) (a) The Chemistry of the Cyano Group; Friedrich, K., Wallenfels,
K., Eds.; Wiley-Interscience: New York, 1970. (b) Tiecco, M.;
Testaferri, L.; Tingoli, M.; Bartoli, D. Tetrahedron 1990, 46, 7139.
(c) Bush, E. J.; Jones, D. W. J. Chem. Soc., Perkin Trans. 1 1997, 3531.
(2) Recent examples: (a) Tsai, A. S.; Bergman, R. G.; Ellman, J. A. J.
Am. Chem. Soc. 2008, 130, 6316. (b) Chen, K.; Baran, P. S. Nature 2009,
459, 824. (c) Stang, E. M.; White, M. C. Nat. Chem. 2009, 1, 547.
(d) Mandal, D.; Yamaguchi, A. D.; Yamaguchi, J.; Itami, K. J. Am. Chem.
Soc. 2011, 133, 19660. (e) Ghosh, A. K.; Cheng, X.; Zhou, B. Org. Lett.
2012, 14, 5046. (f) Rao, H.; Ma, X.; Liu, Q.; Li, Z.; Cao, S.; Li, C.-J. Adv.
Synth. Catal. 2013, 355, 2191. (g) Wang, X.; Li, Z.; Cao, S.; Rao, H. Adv.
Synth. Catal. 2016, 358, 2059.
(3) (a) Leow, D.; Li, G.; Mei, T.-S.; Yu, J.-Q. Nature 2012, 486, 518.
(b) Tang, R.-Y.; Li, G.; Yu, J.-Q. Nature 2014, 507, 215.
(4) (a) Chiong, H. A.; Pham, Q. N.; Daugulis, O. J. Am. Chem. Soc.
2007, 129, 9879. (b) Giri, R.; Maugel, N.; Li, J.-J.; Wang, D.-H.;
Breazzano, S. P.; Saunders, L. B.; Yu, J.-Q. J. Am. Chem. Soc. 2007, 129,
3510.
(5) Representative examples: (a) Wasa, M.; Engle, K. M.; Yu, J.-Q. J.
Am. Chem. Soc. 2009, 131, 9886. (b) Wasa, M.; Engle, K. M.; Lin, D. W.;
Yoo, J.; Yu, J.-Q. J. Am. Chem. Soc. 2011, 133, 19598. (c) Wasa, M.;
Chan, K. S. L.; Zhang, X.; He, J.; Miura, M.; Yu, J.-Q. J. Am. Chem. Soc.
2012, 134, 18570. (d) Deng, Y.; Gong, W.; He, J.; Yu, J.-Q. Angew.
Chem., Int. Ed. 2014, 53, 6692. (e) He, J.; Takise, R.; Fu, H.; Yu, J.-Q. J.
Am. Chem. Soc. 2015, 137, 4618. (f) Chen, G.; Gong, W.; Zhuang, Z.;
(d) Pascal, C.; Dubois, J.; Guen
́
ard, D.; Tchertanov, L.; Thoret, S.;
Gueritte, F. Tetrahedron 1998, 54, 14737.
́
(15) Fleming, F. F.; Yao, L.; Ravikumar, P. C.; Funk, L.; Shook, B. C. J.
Med. Chem. 2010, 53, 7902.
(16) (a) Soli, E. D.; Manoso, A. S.; Patterson, M. C.; Deshong, P.;
Favor, D. A.; Hirschmann, R.; Smith, A. B., III J. Org. Chem. 1999, 64,
3171. (b) Chen, G.; Wang, Z.; Wu, J.; Ding, K. Org. Lett. 2008, 10, 4573.
(17) Narsaiah, A. V.; Nagaiah, K. Adv. Synth. Catal. 2004, 346, 1271.
(18) Stazi, F.; Maton, W.; Castoldi, D.; Westerduin, P.; Curcuruto, O.;
Bacchi, S. Synthesis 2010, 2010, 3332.
(19) (a) Frejd, T.; Klingstedt, T. Synthesis 1987, 1987, 40. (b) Yang, Y.;
Tang, S.; Liu, C.; Zhang, H.; Sun, Z.; Lei, A. Org. Biomol. Chem. 2011, 9,
5343.
(20) (a) Wu, L.; Hartwig, J. F. J. Am. Chem. Soc. 2005, 127, 15824.
(b) Culkin, D. A.; Hartwig, J. F. J. Am. Chem. Soc. 2002, 124, 9330.
(21) Kosugi, M.; Ishiguro, M.; Negishi, Y.; Sano, H.; Migita, T. Chem.
Lett. 1984, 13, 1511.
(22) (a) Shang, R.; Ji, D.-S.; Chu, L.; Fu, Y.; Liu, L. Angew. Chem., Int.
Ed. 2011, 50, 4470. (b) Recio, A., III; Tunge, J. A. Org. Lett. 2009, 11,
5630.
(23) Wu, T.; Mu, X.; Liu, G. Angew. Chem., Int. Ed. 2011, 50, 12578.
(24) Zhang, J.; Liu, Y.; Song, R.; Jiang, G.-F.; Li, J.-H. Synlett 2014, 25,
1031.
Andra, M. S.; Chen, Y.-Q.; Hong, X.; Yang, Y.; Liu, T.; Houk, K. N.; Yu,
̈
J.-Q. Science 2016, 353, 1023.
(6) Zhang, F.-L.; Hong, K.; Li, T.-J.; Park, H.; Yu, J.-Q. Science 2016,
351, 252.
(25) (a) Chatalova-Sazepin, C.; Wang, Q.; Sammis, G. M.; Zhu, J.
Angew. Chem., Int. Ed. 2015, 54, 5443. (b) Li, J.; Wang, Z.; Wu, N.; Gao,
G.; You, J. Chem. Commun. 2014, 50, 15049. (c) Chu, X.; Xu, X.; Meng,
H.; Ji, S.-J. RSC Adv. 2015, 5, 67829. (d) Li, Z.; Xiao, Y.; Liu, Z. Chem.
Commun. 2015, 51, 9969. (e) Zhou, D.; Li, Z.; Li, J.; Li, S.; Wang, M.;
Luo, X.; Ding, G.; Sheng, R.; Fu, M.; Tang, S. Eur. J. Org. Chem. 2015,
2015, 1606. (f) Chu, X.; Xing, Z.; Meng, H.; Xu, X.; Ji, S. Org. Chem.
Front. 2016, 3, 165.
(7) Representative examples: (a) Stowers, K. J.; Fortner, K. C.;
Sanford, M. S. J. Am. Chem. Soc. 2011, 133, 6541. (b) Giri, R.; Lan, Y.;
Liu, P.; Houk, K. N.; Yu, J.-Q. J. Am. Chem. Soc. 2012, 134, 14118.
(8) Simmons, E. M.; Hartwig, J. F. Nature 2012, 483, 70.
(9) The concerns in removing potentially toxic trace noble transition-
metal catalysts from the end products always exist in drug discoveries
because trace metals in products for human consumption are heavily
(26) Pan, C.; Zhang, H.; Zhu, C. Org. Biomol. Chem. 2015, 13, 361.
(27) Li, X.; Xu, J.; Gao, Y.; Fang, H.; Tang, G.; Zhao, Y. J. Org. Chem.
2015, 80, 2621.
́ ́
regulated by international bodies; see: Legare, M.-A.; Courtemanche,
́
M.-A.; Rochette, E.; Fontaine, F.-G. Science 2015, 349, 513.
(10) The requisition of pre-established functional groups may lead to
poor step- and atom-economies; moreover, the operational complexities
associated with synthesizing and using these functionalized substrates
may hinder their widespread adoption; see: Johnston, C. P.; Smith, R.
T.; Allmendinger, S.; MacMillan, D. W. C. Nature 2016, 536, 322.
(11) Li’s group reported pioneering studies on dehydrogenative
C(sp3)−C bond-forming reactions. Representative examples: (a) Li, Z.;
Li, C.-J. J. Am. Chem. Soc. 2004, 126, 11810. (b) Li, Z.; Li, C.-J. J. Am.
Chem. Soc. 2005, 127, 6968. (c) Li, Z.; Li, C.-J. J. Am. Chem. Soc. 2005,
127, 3672. (d) Li, Z.; Li, C.-J. J. Am. Chem. Soc. 2006, 128, 56. (e) Zhang,
(28) (a) Ni, Z.; Huang, X.; Wang, J.; Pan, Y. RSC Adv. 2016, 6, 522.
(b) Lan, X.-W.; Wang, N.-X.; Bai, C.-B.; Lan, C.-L.; Zhang, T.; Chen, S.-
L.; Xing, Y. Org. Lett. 2016, 18, 5986.
(29) Previously, zolpidem was prepared through a six-step procedure
starting from 6-methyl-2-(p-tolyl)imidazo[1,2-a]pyridine 3 in about
25% yield; see: : Jasty, A. M.; Tamma, R. R.; Mohanarangam, S.;
Yasareni, S.; Rupakala, G. S.; Debashish, G. US 2007/0027180, 2007.
D
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