Organic Letters
Letter
́
(3) (a) Beladhria, A.; Yuan, K.; Ben Ammar, H.; Soule, J.-F.; Ben
3aa was fully inhibited (Scheme 4, eq 5), suggesting that an
interaction between Mg2+ and the sulfinate may activate the C−
Salem, R.; Doucet, H. Synthesis 2014, 46, 2515−2523. (b) Jin, R.; Yuan,
́
K.; Chatelain, E.; Soule, J.-F.; Doucet, H. Adv. Synth. Catal. 2014, 356,
In conclusion, we have developed a transition-metal-free15
cross-coupling reaction of heteroaryl sulfinates with Grignard
reagents that provides an efficient method to synthesize
heterobiaryls under mild conditions. In this reaction, the
heteroaryl sulfinates were employed as electrophilic substrates
in a nucleophilic substitution reaction, and we anticipate this will
expand the future use of heteroaryl sulfinates in organic
chemistry.
3831−3841. (c) Zhang, W.; Liu, F.; Zhao, B. Appl. Organomet. Chem.
́
2015, 29, 524−527. (d) Yuan, K.; Sang, R.; Soule, J.-F.; Doucet, H.
Catal. Sci. Technol. 2015, 5, 2904−2912. (e) Loukotova, L.; Yuan, K.;
Doucet, H. ChemCatChem 2014, 6, 1303−1309. (f) Hfaiedh, F.; Yuan,
́
K.; Ben Ammar, H.; Ben Hassine, B.; Soule, J.-F.; Doucet, H.
ChemSusChem 2015, 8, 1794−1804. (g) Rao Volla, C. M.; Vogel, P.
Angew. Chem., Int. Ed. 2008, 47, 1305−1307.
(4) (a) Yu, X.; Li, X.; Wan, B. Org. Biomol. Chem. 2012, 10, 7479−
7482. (b) Chen, W.; Chen, H.; Xiao, F.; Deng, G.-J. Org. Biomol. Chem.
2013, 11, 4295−4298. (c) Miao, H.; Wang, F.; Zhou, S.; Zhang, G.; Li,
Y. Org. Biomol. Chem. 2015, 13, 4647−4651. (d) Zhong, S.; Sun, C.;
Dou, S.; Liu, W. RSC Adv. 2015, 5, 27029−27033. (e) Huang, L.; Qi, J.;
Wu, X.; Wu, W.; Jiang, H. Chem. - Eur. J. 2013, 19, 15462−15466.
(f) Yuen, O. Y.; So, C. M.; Wong, W. T.; Kwong, F. Y. Synlett 2012, 23,
2714−2718. (g) Liu, B.; Li, J.; Song, F.; You, J. Chem. - Eur. J. 2012, 18,
10830−10833. (h) Yang, F.-L.; Ma, X.-T.; Tian, S.-K. Chem. - Eur. J.
2012, 18, 1582−1585.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
Experimental procedures and characterization data for
(5) Rattanangkool, E.; Sukwattanasinitt, M.; Wacharasindhu, S. J. Org.
Chem. 2017, 82, 13256−13262.
(6) Murray, S. G.; Hartley, F. R. Chem. Rev. 1981, 81, 365−414.
(7) Yang, B.; Wang, Z.-X. Org. Lett. 2017, 19, 6220−6223.
(8) Li, Y.; Yang, W.; Cheng, G.; Yang, D. J. Org. Chem. 2016, 81,
4744−4750.
AUTHOR INFORMATION
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Corresponding Authors
ORCID
(9) (a) Martin, C.; Sandrinelli, F.; Perrio, C.; Perrio, S.; Lasne, M. C. J.
Org. Chem. 2006, 71, 210−214. (b) Shavnya, A.; Coffey, S. B.; Hesp, K.
D.; Ross, S. C.; Tsai, A. S. Org. Lett. 2016, 18, 5848−5851. (c) Yang, K.;
Ke, M.; Lin, Y.; Song, Q. Green Chem. 2015, 17, 1395−1399.
(10) (a) Davies, A. T.; Curto, J. M.; Bagley, S. W.; Willis, M. C. Chem.
Sci. 2017, 8, 1233−1237. (b) Dong, J.; Krasnova, L.; Finn, M. G.;
Sharpless, K. B. Angew. Chem., Int. Ed. 2014, 53, 9430−9448.
(11) (a) Riendeau, D.; Percival, M. D.; Brideau, C.; Charleson, S.;
Dube, D.; Ethier, D.; Falgueyret, J. P.; Friesen, R. W.; Gordon, R.;
Greig, G.; Guay, J.; Mancini, J.; Ouellet, M.; Wong, E.; Xu, L.; Boyce, S.;
Visco, D.; Girard, Y.; Prasit, P.; Zamboni, R.; Rodger, I. W.; Gresser, M.;
Ford-Hutchinson, A. W.; Young, R. N.; Chan, C.-C. Br. J. Pharmacol.
2001, 296, 558−566. (b) Xie, Y.; Chi, H.-W.; Guan, A.-Y.; Liu, C.-L.;
Ma, H.-J.; Cui, D.-L. Bioorg. Med. Chem. 2016, 24, 428−434. (c) Burt,
T. D.; Agan, B. K.; Marconi, V. C.; He, W.; Kulkarni, H.; Mold, J. E.;
Cavrois, M.; Huang, Y.; Mahley, R. W.; Dolan, M. J.; McCune, J. M.;
Ahuja, S. K. Proc. Natl. Acad. Sci. U. S. A. 2008, 105, 8718−8723. (d) Li,
Y.; Zhou, D.; Ferguson, S. S.; Dorff, P.; Simpson, T. R.; Grimm, S. W.
Xenobiotica 2010, 40, 721−729. (e) Croom, K. F.; Dhillon, S.; Keam, S.
J. Drugs 2009, 69, 1107−1140.
(12) (a) Someya, C. I.; Weidauer, M.; Enthaler, S. Catal. Lett. 2013,
143, 424−431. (b) Yoshikai, N.; Matsuda, H.; Nakamura, E. J. Am.
Chem. Soc. 2009, 131, 9590−9599.
(13) (a) Shirakawa, E.; Hayashi, Y.; Itoh, K.; Watabe, R.; Uchiyama,
N.; Konagaya, W.; Masui, S.; Hayashi, T. Angew. Chem., Int. Ed. 2012,
51, 218−221. (b) Uchiyama, N.; Shirakawa, E.; Hayashi, T. Chem.
Commun. 2013, 49, 364−366. (c) Hill, R. R.; Rychnovsky, S. D. J. Org.
Chem. 2016, 81, 10707−10714.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the National Basic Research
Program of China (2015CB931900), the National Natural
Science Foundation of China (21672187, 21632009, 21421002,
21472221), the Key Programs of the Chinese Academy of
Sciences (KGZD-EW-T08), the Key Research Program of
Frontier Sciences of CAS (QYZDJ-SSW-SLH049), Shanghai
Science and Technology program (16QA1404600), and ZJNSF
(LZ17H300002).
REFERENCES
■
(1) (a) Cremlyn, R. J. An Introduction to Organosulfur Chemistry;
Wiley: New York, 1996. (b) Ruano, J. L. G.; de la Plata, B. C. In
Organosulfur Chemistry I; Page, P. C. B., Ed.; Springer: Heidelberg,
1999; p 1. (c) Furukawa, N.; Sato, S. In Organosulfur Chemistry II; Page,
P. C. B., Ed.; Springer: Heidelberg, 1999; p 89. (d) Rayner, C. M.
Advances in Sulfur Chemistry; JAI Press: Greenwich, 2000; Vol. 2.
(2) (a) Taniguchi, N. Synlett 2013, 24, 2571−2574. (b) Markovic, T.;
Rocke, B. N.; Blakemore, D. C.; Mascitti, V.; Willis, M. C. Chem. Sci.
2017, 8, 4437−4442. (c) Markovic, T.; Rocke, B. N.; Blakemore, D. C.;
Mascitti, V.; Willis, M. C. Org. Lett. 2017, 19, 6033−6035. (d) Ortgies,
D. H.; Hassanpour, A.; Chen, F.; Woo, S.; Forgione, P. Eur. J. Org.
(14) (a) Bunnett, J. F.; Zahler, R. E. Chem. Rev. 1951, 49, 273−412.
(b) Buncel, E.; Dust, J. M.; Terrier, F. Chem. Rev. 1995, 95, 2261−2280.
(15) ICP-OES analysis of the reaction mixture showed that there was
less than 1 ppm (within the detection limit) of Co, Ni, Cu, and Pd and
26 ppm of Fe. To rule out the effect of Fe, the reaction was conducted in
the presence of FeCl3 (5 mol %) to give 20% yield of 3aa accompanied
by biphenyl as a major product (see the SI). This fact shows that Fe
drastically lowered the yield of 3aa, so it is unlikely that the trace
amount of Fe is involved in the coupling reaction between heteroaryl
sulfinates and Grignard reagents.
́
Chem. 2016, 2016, 408−425. (e) Sevigny, S.; Forgione, P. Chem. - Eur.
J. 2013, 19, 2256−2260. (f) Zhao, F.; Tan, Q.; Xiao, F.; Zhang, S.;
Deng, G.-J. Org. Lett. 2013, 15, 1520−1523. (g) Chen, J.; Li, J.; Su, W.
Molecules 2014, 19, 6439−6449. (h) Liu, S.; Chen, J.; Zhang, R.; Zhao,
F.; Deng, G.-J. Asian J. Org. Chem. 2014, 3, 1150−1153. (i) Liu, J.;
Zhou, X.; Rao, H.; Xiao, F.; Li, C.-J.; Deng, G.-J. Chem. - Eur. J. 2011, 17,
̈
7996−7999. (j) Skillinghaug, B.; Skold, C.; Rydfjord, J.; Svensson, F.;
̈
̈
Behrends, M.; Savmarker, J.; Sjoberg, P. J. R.; Larhed, M. J. Org. Chem.
2014, 79, 12018−12032. (k) Cheng, K.; Hu, S.; Zhao, B.; Zhang, X.-M.;
Qi, C. J. Org. Chem. 2013, 78, 5022−5025. (l) Zhou, C.; Liu, Q.; Li, Y.;
Zhang, R.; Fu, X.; Duan, C. J. Org. Chem. 2012, 77, 10468−10472.
D
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