Organic Letters
Letter
mol−1), and internal reaction coordinate analysis is provided in
Figure S4. Notably, the formation of B2a is also thermody-
namically favored and is the most exothermic process (−91.8
kcal mol−1). (2) In the case of 3j (path b), the release of
thiophene C3j from IM2(3j)·Cs+ is kinetically more favored,
as it has the lowest energy barrier of 10.2 kcal mol−1.
(3) (a) Asamdi, M.; Chikhalia, K. H. Asian J. Org. Chem. 2017, 6,
1331. (b) Yoshida, H.; Takaki, K. Synlett 2012, 23, 1725. (c) Pena,
̃
́
́
D.; Perez, D.; Guitian, E. Angew. Chem., Int. Ed. 2006, 45, 3579.
(4) (a) Wu, C.; Yang, Y.; Shi, F. Youji Huaxue 2015, 35, 770.
(b) Miyabe, H. Curr. Org. Chem. 2015, 19, 1222. (c) Yoshioka, E.;
Miyabe, H. Tetrahedron 2012, 68, 179. (d) Okuma, K. Heterocycles
2012, 85, 515.
In summary, we have developed two desulfurization
reactions by simply treating diaryl or heteroaryl sulfoxides
with benzyne, which produce biaryls or desulfurized
heterarenes, respectively. The reaction to prepare biaryls B2
proceeded under mild conditions and exhibited excellent
functional group compatibility. However, diphenyl sulfoxide 1a
and diaryl sulfoxides 1b−1d bearing electron-donating groups
are unsuitable for the reaction. Unlike diaryl sulfoxides 1 and 2,
heteroaryl sulfoxides 3 including indoles, benzothiophenes,
benzofurans, and thiophenes afford desulfurized heteroarenes
C3. Control experiments and DFT studies proposed that
tetraaryl(heteroaryl) sulfuranes IM2 were formed in both
reactions. Due to their different electronic properties, the
sulfurane intermediates (IM2) undergo distinct disassembly
processes to deliver biaryls (B2) and desulfurized heterarenes
(C3), respectively. Synthetic applications and further explora-
tion of benzyne insertion reactions are underway in our
laboratory.
(5) Matsuzawa, T.; Yoshida, S.; Hosoya, T. Tetrahedron Lett. 2018,
59, 4197.
(6) Liu, F.-L.; Chen, J.-R.; Zou, Y.-Q.; Wei, Q.; Xiao, W.-J. Org. Lett.
2014, 16, 3768.
(7) Li, H.-Y.; Xing, L.-J.; Lou, M.-M.; Wang, H.; Liu, R.-H.; Wang,
B. Org. Lett. 2015, 17, 1098.
(8) Li, Y.; Qiu, D.; Gu, R.; Wang, J.; Shi, J.; Li, Y. J. Am. Chem. Soc.
2016, 138, 10814.
(9) Li, Y.; Studer, A. Org. Lett. 2017, 19, 666.
(10) Matsuzawa, T.; Uchida, K.; Yoshida, S.; Hosoya, T. Org. Lett.
2017, 19, 5521.
(11) Li, X.; Sun, Y.; Huang, X.; Zhang, L.; Kong, L.; Peng, B. Org.
Lett. 2017, 19, 838.
(12) For selected examples on biaryl synthesis from aryl sulfoxides,
see: (a) Yamamoto, K.; Otsuka, S.; Nogi, K.; Yorimitsu, H. ACS Catal.
́
2017, 7, 7623. (b) Christensen, P. R.; Patrick, B. O.; Caron, E.; Wolf,
M. O. Angew. Chem., Int. Ed. 2013, 52, 12946. (c) Melzig, L.; Rauhut,
C. B.; Naredi-Rainer, N.; Knochel, P. Chem. - Eur. J. 2011, 17, 5362.
(13) For selected examples on desulfurization of heteraryl sulfoxides,
see: (a) Gladow, D.; Reissig, H.-U. J. Org. Chem. 2014, 79, 4492.
̈
(b) Samann, C.; Coya, E.; Knochel, P. Angew. Chem., Int. Ed. 2014,
53, 1430. (c) Vogt, E.-J.; Zapol’skii, V. A.; Nutz, E.; Kaufmann, D. E.
Eur. J. Org. Chem. 2013, 20, 4285.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
■
S
(14) Our previously reported synthesis of triarylsulfonium salts
(Scheme 1, eq 5) were also studied by DFT calculations. For details,
see Figure S1. Similar to path b, the reaction (path c) of 1a also
proceeds via formation of IM2(1a) and subsequent protonation by
MeCN.
(15) For selected examples on reactions of tetraaryl sulfuranes, see:
(a) Sato, S.; Ameta, H.; Horn, E.; Takahashi, O.; Furukawa, N. J. Am.
Chem. Soc. 1997, 119, 12374. (b) Oae, S.; Ishihara, H.; Yoshihara, M.
Chem. Heterocycl. Compd. 1995, 31, 917. (c) Furukawa, N.;
Matsunaga, Y.; Sato, S. Synlett 1993, 9, 655. For a recent example
on heterobiaryl synthesis via P(V) intermediates, see: Hilton, M. C.;
Zhang, X.; Boyle, B. T.; Alegre-Requena, J. V.; Paton, R. S.; McNally,
A. Science 2018, 362, 799.
Experimental procedures, compound characterization,
1
and copies of H NMR and 13C NMR spectra (PDF)
AUTHOR INFORMATION
■
Corresponding Author
ORCID
Author Contributions
§D.L.C. and Y.S. contributed equally.
Notes
(16) Bersuker, I. B. Chem. Rev. 2013, 113, 1351.
(17) For a recent example on cesium−arene interactions, see: Spisak,
S. N.; Zabula, A. V.; Alkan, M.; Filatov, A. S.; Rogachev, A. Y.;
Petrukhina, M. A. Angew. Chem., Int. Ed. 2018, 57, 6171.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful for financial support from the National Natural
Science Foundation of China (NSFC-21502171) and the
support of the Natural Science Foundation of Zhejiang
Province, China (LY17B060001).
REFERENCES
■
(1) For selected reviews on synthetic applications of arynes, see:
(a) Goetz, A. E.; Shah, T. K.; Garg, N. K. Chem. Commun. 2015, 51,
34. (b) Gampe, C. M.; Carreira, E. M. Angew. Chem., Int. Ed. 2012,
51, 3766. (c) Tadross, P. M.; Stoltz, B. M. Chem. Rev. 2012, 112,
3550.
(2) For selected reviews on aryne chemistry, see: (a) Roy, T.; Biju,
A. T. Chem. Commun. 2018, 54, 2580. (b) Shi, J.; Li, Y.; Li, Y. Chem.
Soc. Rev. 2017, 46, 1707. (c) Yoshida, S.; Hosoya, T. Chem. Lett.
2015, 44, 1450. (d) Wu, C.- R.; Shi, F. Asian J. Org. Chem. 2013, 2,
116.
D
Org. Lett. XXXX, XXX, XXX−XXX