Journal of the American Chemical Society
Communication
(b) Newhouse, T.; Baran, P. S. Angew. Chem., Int. Ed. 2011, 50, 3362.
(c) Lyons, T. W.; Sanford, M. S. Chem. Rev. 2010, 110, 1147. (d) Colby,
D. A.; Bergman, R. G.; Ellman, J. A. Chem. Rev. 2010, 110, 624. (e) Sun,
C.-L.; Li, B.-J.; Shi, Z.-J. Chem. Rev. 2011, 111, 1293. The elegant study
on benzylic C−H arylation with limiting alkylarene reagents: (f) Zhang,
F.-L.; Hong, K.; Li, T.-J.; Park, H.; Yu, J.-Q. Science 2016, 351, 252.
(g) He, J.; Li, S.; Deng, Y.; Fu, H.; Laforteza, B. N.; Spangler, J. E.; Homs,
A.; Yu, J.-Q. Science 2014, 343, 1216. Other examples: (h) Wasa, M.;
Chan, K. S. L.; Zhang, X.-G.; He, J.; Miura, M.; Yu, J.-Q. J. Am. Chem. Soc.
2012, 134, 18570. (i) Shabashov, D.; Daugulis, O. J. Am. Chem. Soc.
2010, 132, 3965. (j) Zaitsev, V. G.; Shabashov, D.; Daugulis, O. J. Am.
Chem. Soc. 2005, 127, 13154. (k) Wang, H.; Tong, H.-R.; He, G.; Chen,
G. Angew. Chem., Int. Ed. 2016, 55, 15387.
(5) (a) Ortiz de Montellano, P. R. Chem. Rev. 2010, 110, 932.
(b) Meunier, B.; de Visser, S. P.; Shaik, S. Chem. Rev. 2004, 104, 3947.
(6) (a) Che, C. M.; Lo, V. K. Y.; Zhou, C. Y.; Huang, J. S. Chem. Soc.
Rev. 2011, 40, 1950. (b) Stavropoulos, P.; Celenligil-Cetin, R.; Tapper,
A. E. Acc. Chem. Res. 2001, 34, 745. (c) Brothers, P. J.; Collman, J. P. Acc.
Chem. Res. 1986, 19, 209.
and arylboronic acids and excellent functional group compati-
bilities make this method an ideal tool to achieve late-stage
arylation of bioactive compounds. Further mechanism inves-
tigations of the mechanism and asymmetric reaction are in
progress in our group.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
■
S
Syntheses, characterization, and additional data (PDF)
X-ray crystallographic data for 3s (CCDC 1549166), 6j
(CCDC 1549168), and 6p (CCDC 1549169) (CIF)
AUTHOR INFORMATION
Corresponding Author
■
(7) (a) Milan, M.; Bietti, M.; Costas, M. ACS Cent. Sci. 2017, 3, 196.
(b) Zhang, R.; Yu, W. Y.; Lai, T. S.; Che, C. M. Chem. Commun. 1999,
1791. (c) Groves, J. T.; Viski, P. J. Am. Chem. Soc. 1989, 111, 8537.
(8) Liu, W.; Groves, J. T. Acc. Chem. Res. 2015, 48, 1727.
ORCID
Notes
The authors declare no competing financial interest.
(9) (a) Dydio, P.; Key, H. M.; Hayashi, H.; Clark, D. S.; Hartwig, J. F. J.
Am. Chem. Soc. 2017, 139, 1750. (b) Karimov, R. R.; Sharma, A.;
Hartwig, J. F. ACS Cent. Sci. 2016, 2, 715. (c) Huang, X.; Bergsten, T.;
Groves, J. T. J. Am. Chem. Soc. 2015, 137, 5300. (d) Ni, Z.; Zhang, Q.;
Xiong, T.; Zheng, Y.; Li, Y.; Zhang, H.; Zhang, J.; Liu, Q. Angew. Chem.,
Int. Ed. 2012, 51, 1244. (e) Wiese, S.; Badiei, Y. M.; Gephart, R. T.;
Mossin, S.; Varonka, M. S.; Melzer, M. M.; Meyer, K.; Cundari, T. R.;
Warren, T. H. Angew. Chem., Int. Ed. 2010, 49, 8850. (f) Gephart, R. T.;
Huang, D. L.; Aguila, M. J.; Schmidt, G.; Shahu, A.; Warren, T. H. Angew.
Chem., Int. Ed. 2012, 51, 6488.
(10) (a) Shaw, M. H.; Shurtleff, V. W.; Terrett, J. A.; Cuthbertson, J. D.;
MacMillan, D. W. C. Science 2016, 352, 1304. (b) Heitz, D. R.; Tellis, J.
C.; Molander, G. A. J. Am. Chem. Soc. 2016, 138, 12715. (c) Shields, B. J.;
Doyle, A. G. J. Am. Chem. Soc. 2016, 138, 12719. (d) Zuo, Z.; Ahneman,
D. T.; Chu, L.; Terrett, J. A.; Doyle, A. G.; MacMillan, D. W. C. Science
2014, 345, 437. (e) Liu, D.; Liu, C.; Li, H.; Lei, A. Angew. Chem., Int. Ed.
2013, 52, 4453. (f) Liu, D.; Li, Y.; Qi, X.; Liu, C.; Lan, Y.; Lei, A. Org.
Lett. 2015, 17, 998. (g) Li, Y.; Li, B.-J.; Lu, X.-Y.; Lin, S.; Shi, Z.-J. Angew.
Chem., Int. Ed. 2009, 48, 3817.
(11) Late-stage C−H functionalization of drug-like molecules: Cernak,
T.; Dykstra, K. D.; Tyagarajan, S.; Vachal, P.; Krska, S. W. Chem. Soc. Rev.
2016, 45, 546.
(12) (a) Zhang, W.; Wang, F.; McCann, S. D.; Wang, D.; Chen, P.;
Stahl, S. S.; Liu, G. Science 2016, 353, 1014. (b) Wang, F.; Wang, D.;
Wan, X.; Wu, L.; Chen, P.; Liu, G. J. Am. Chem. Soc. 2016, 138, 15547.
(c) Wang, D.; Wang, F.; Chen, P.; Lin, Z.; Liu, G. Angew. Chem., Int. Ed.
2017, 56, 2054.
ACKNOWLEDGMENTS
■
We are grateful for financial support from the National Basic
Research Program of China (973-2015CB856600), the National
Nature Science Foundation of China (Nos. 21532009,
21421091, and 21472219), Program of Shanghai Academic/
Technology Research Leader (17XD1404500), and the Strategic
Priority Research Program of the Chinese Academy of Sciences
(No. XDB20000000). This research was also partially supported
by CAS Interdisciplinary Innovation Team. We thank Bide
Pharmatech Ltd for the generous gift of Dapagliflozin.
REFERENCES
■
(1) (a) McNally, D. J.; Wurms, K. V.; Labbe, C.; Quideau, S.; Belanger,
R. R. J. Nat. Prod. 2003, 66, 1280. (b) Liang, H.; Wu, X.; Yalowich, J. C.;
Hasinoff, B. B. Mol. Pharmacol. 2007, 73, 686. (c) Cheltsov, A. V.;
Aoyagi, M.; Aleshin, A.; Yu, E. C.-W.; Gilliland, T.; Zhai, D.; Bobkov, A.
A.; Reed, J. C.; Liddington, R. C.; Abagyan, R. J. Med. Chem. 2010, 53,
3899. (d) Zhang, J.; Xiong, B.; Zhen, X.; Zhang, A. Med. Res. Rev. 2009,
29, 272.
(2) Selected examples of the synthesis of 1,1-diarylalkenes: (a) Wang,
Z.; Ai, F.; Wang, Z.; Zhao, W.; Zhu, G.; Lin, Z.; Sun, J. J. Am. Chem. Soc.
2015, 137, 383. (b) Wang, Z.-Q.; Feng, C.-G.; Zhang, S.-S.; Xu, M.-H.;
Lin, G.-Q. Angew. Chem., Int. Ed. 2010, 49, 5780. (c) Paquin, J. F.;
Defieber, C.; Stephenson, C. R. J.; Carreira, E. M. J. Am. Chem. Soc. 2005,
127, 10850. (d) Friis, S. D.; Pirnot, M. T.; Buchwald, S. L. J. Am. Chem.
Soc. 2016, 138, 8372. (e) Logan, K. M.; Smith, K. B.; Brown, M. K.
Angew. Chem., Int. Ed. 2015, 54, 5228.
(3) Some recent examples: (a) Zhou, Q.; Cobb, K. M.; Tan, T.;
Watson, M. P. J. Am. Chem. Soc. 2016, 138, 12057. (b) Gutierrez, O.;
Tellis, J. C.; Primer, D. N.; Molander, G. A.; Kozlowski, M. C. J. Am.
Chem. Soc. 2015, 137, 4896. (c) Do, H.-Q.; Chandrashekar, E. R. R.; Fu,
G. C. J. Am. Chem. Soc. 2013, 135, 16288. (d) Zhou, Q.; Srinivas, H. D.;
Dasgupta, S.; Watson, M. P. J. Am. Chem. Soc. 2013, 135, 3307.
(e) Wisniewska, H. M.; Swift, E. C.; Jarvo, E. R. J. Am. Chem. Soc. 2013,
135, 9083. (f) Taylor, B. L. H.; Swift, E. C.; Waetzig, J. D.; Jarvo, E. R. J.
Am. Chem. Soc. 2011, 133, 389. (g) Binder, J. T.; Cordier, C. J.; Fu, G. C.
J. Am. Chem. Soc. 2012, 134, 17003. (h) Choi, J.; Fu, G. C. J. Am. Chem.
Soc. 2012, 134, 9102. (i) Wilsily, A.; Tramutola, F.; Owston, N. A.; Fu,
G. C. J. Am. Chem. Soc. 2012, 134, 5794. (j) Oelke, A. J.; Sun, J.; Fu, G. C.
J. Am. Chem. Soc. 2012, 134, 2966.
(13) (a) Wang, F.; Wang, D.; Mu, X.; Chen, P.; Liu, G. J. Am. Chem. Soc.
2014, 136, 10202. (b) Wu, L.; Wang, F.; Wan, X.; Wang, D.; Chen, P.;
Liu, G. J. Am. Chem. Soc. 2017, 139, 2904.
(14) For more details, see the Supporting Information.
(15) With the optimized reaction conditions, the Box ligand still
exhibited poor reactivity toward arylation of 1a (<30% yield).
(16) The reactions of p-RC6H4B(OH)2 provided the desired products
in 30% (R = Me), 22% (R = tBu), and <5% yield (R = OMe).
(17) Fieser, L. F.; Cason, J. J. Am. Chem. Soc. 1940, 62, 432.
(18) Foster, M. FDA Panel Advises Against Approval of Dapagliflozin.
Healio, Endocrine Today, July 19, 2011.
(19) Bedalov, A.; Gatbonton, T.; Irvine, W. P.; Gottschling, D. E.;
Simon, J. A. Proc. Natl. Acad. Sci. U. S. A. 2001, 98, 15113.
(20) Neugebauer, R. C.; Uchiechowska, U.; Meier, R.; Hruby, H.;
Valkov, V.; Verdin, E.; Sippl, W.; Jung, M. J. Med. Chem. 2008, 51, 1203.
(21) Khan, P. M.; El-Gendy, B. E.-D. M.; Kumar, N.; Garcia-Ordonez,
R.; Lin, L.; Ruiz, C. H.; Cameron, M. D.; Griffin, P. R.; Kamenecka, T.
M. Bioorg. Med. Chem. Lett. 2013, 23, 532.
(4) Some reviews of C−H bond activation: (a) Giri, R.; Shi, B. F.;
Engle, K. M.; Maugel, N.; Yu, J.-Q. Chem. Soc. Rev. 2009, 38, 3242.
D
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX