Chemistry - An Asian Journal
10.1002/asia.201700017
FULL PAPER
illustrated in Scheme 4. However, further research is required to
determine the exact details of this reaction.
g) M. L. Louillat, F. W. Patureau, Chem. Soc. Rev. 2014, 43, 901; h) J.
Jiao, K. Murakami, K. Itami, ACS Catal. 2016, 6, 610.
[
3] a) P. P. Dixit, P. S. Nair, V. J. Patil, S. Jain, S. K. Arora, N. Sinha, Bioorg.
Med. Chem. Lett. 2005, 15, 3002; b) N. Mishra, P. Arora, B. Kumar, L. C.
Mishra, A. Bhattacharya, S. K. Awasthi, V. K. Bhasin, Eur. J. Med. Chem.
2008, 43, 1530; c) Z. Rezaei, S. Khabnadideh, K. Pakshir, Z. Hossaini, F.
Amiri, E. Assadpour, Eur. J. Med. Chem. 2009, 44, 3064; d) R. K. Kumar,
M. A. Ali, T. Punniyamurthy, Org. Lett. 2011, 13, 2102.
[
[
4] a) P. A. Bonnet, R. K. Robins, J. Med. Chem. 1993, 36, 635; b) D. M.
Huryn, M. Okabe, Chem. Rev. 1992, 92, 1745; c) K. A. Jacobson, P. J. M.
van Galen, M. Williams, J. Med. Chem. 1992, 35, 407.
Scheme 4. Proposed mechanism.
5] For selected papers on difunctionalization of alkenes, see: a) Y. Shimizu,
M. Kanai, Tetrahedron Lett. 2014, 55, 3727; b) H. Egami, M. Sodeoka,
Angew. Chem. 2014, 126, 8434; Angew. Chem. Int. Ed. 2014, 53, 8294;
c) R.-J. Song, Y. Liu, Y.-X. Xie, J.-H. Li, Synthesis 2015, 47, 1195; d) M.-
Y. Cao, X. Ren, Z. Lu, Tetrahedron Lett. 2015, 56, 3732; e) H.-M. Wang,
Q.-Q Lu, C.-H. Qian, C. Liu, W. Liu, K. Chen, A. Lei, Angew. Chem. Int.
Ed. 2016, 128, 1106; Angew. Chem. Int. Ed. 2016, 55, 1094; f) H.-M.
Wang, G.-Y. Wang, Q.-Q. Lu, C. Chiang, P. Peng, J.-F. Zhou, A. Lei,
Chem. Eur. J. 2016, 22, 14489.
Conclusions
In summary, we have described a metal-free protocol for
amidoselenation and amidotelluration of alkenes with dioxygen
as the terminal oxidant. This reaction is compatible with a broad
range of nitrogen and selenium sources, and afforded a series of
structurally diverse β-amido-selenides and β-amido-tellurides in
moderate to high yields. Preliminary mechanistic studies support
a classic onium ion pathway. The broad substrate scope, ready
availability of reagents, potential for adaption to large-scale
preparations, and ease of product derivatization make this an
attractive protocol for both academic and industrial use.
[
6] For recent examples, see: a) H.-W. Zhang, W.-Y. Pu, T. Xiong, Y. Li, X.
Zhou, K. Sun, Q. Liu, Q. Zhang, Angew. Chem. 2013, 125, 2589; Angew.
Chem. Int. Ed. 2013, 52, 2529; b) S. Qiu, T. Xu, J. Zhou, Y. Guo, G.-S.
Liu, J. Am. Chem. Soc. 2010, 132, 2856; c) B. Zhang, A. Studer, Org. Lett.
2014, 16, 1790; d) H.-W. Zhang, Y.-C. Song, J.-B. Zhao, J.-P. Zhang, Q.
Zhang, Angew. Chem. 2014, 126, 11259; Angew. Chem. Int. Ed. 2014, 53,
1
1079; e) R. Sakae, K. Hirano, M. Miura, J. Am. Chem. Soc. 2015, 137,
460; f) A. E. Strom, D. Balcells, J. F. Hartwig, ACS Catal. 2016, 6, 5651.
6
Experimental Section
g) J. A. Jr. Gurak, K. S. Yang, Z. Liu, K. M. Engle, J. Am. Chem. Soc.
016, 138, 5805.
2
Styrene 1a (0.55 mmol, 57.2 mg), 1H-benzo[d][1,2,3]triazole 2a (0.5
mmol, 59.5 mg) and diphenyl diselenide 3a (0.5 mmol, 156.0 mg) were
added to a Schlenk tube with an O -filled balloon was connected to the
2
side arm. The mixture was stirred at 60 °C for 12.0 h, upon completion of
the reaction (as monitored by TLC), the mixture was cooled to room
temperature and quenched with water before extraction with
dichloromethane (5 × 3 mL). The combined organic layers were dried
[7] For recent examples, see: a) B. Zhang, A. Studer, Org. Lett. 2013, 15,
4548; b) R. M. Romero, T. H. Wꢀste, K. Muꢁiz, Chem.–Asian J. 2014, 9,
972; c) K. B. Hong, J. N. Johnston, Org. Lett. 2014, 16, 3804; d) Y. Li, M.
Hartmann, C. G. Daniliuca, A. Studer, Chem. Commun. 2015, 51, 5706; e)
K. K. Rajbongshi, I. Saikia, L. D. Chanu, S. Roy, P. Phukan, J. Org. Chem.
2016, 81, 5423; f) H. Chen, A. Kaga. S. Chiba, Org. Biomol. Chem. 2016,
14, 5481.
over anhydrous Na
2
SO
4
and concentrated under reduced pressure to
[8] a) C. Paulmier, Selenium Reagents and Intermediates in Organic
Synthesis; Pergamon: Oxford, U.K., 1986; b) S. Patai, Z. Rappoport, The
Chemistry of Organic Selenium and Tellurium Compounds; Wiley: New
York, 1986; c) D. Liotta, Organoselenium Chemistry; Wiley: New York,
give a residue, which was purified by flash column chromatography over
silica gel (EtOAc/petroleum ether = 1:6, v/v) to give compound 4a (161.1
mg) in 85% yield.
1
987; d) A. Krief, L. Hevesi, Organoselenium Chemistry I; Springer: Berlin,
988; e) T. G. Back, Organoselenium Chemistry: A Pratical Approach;
1
Oxford University Press: Oxford, U.K., 1999; f) D. Liotta, Acc. Chem. Res.
984, 17, 28; g) T. Wirth, Organoselenium Chemistry–Modern
Acknowledgements
1
Developments in Organic Synthesis; Topics in Current Chemistry 208,
SpringVerlag: Heidelberg, Germany, 2000; h) G. Mugesh, H. B. Singh,
Acc. Chem. Res. 2002, 35, 226.
This work was supported by the National Natural Science
Foundation of China (U1504210) and Program for Innovative
Research Team of Science and Technology in the University of
Henan Province (16IRTSTHN003).
[
[
[
[
9] A. Toshimitsu, T. Aoai, H. Owada, S. Uemura, M. Okano, J. Org. Chem.
1981, 46, 4727.
10] Y. Zheng, Y. He, G.-W. Rong, X.-L. Zhang, Y.-C. Weng, K.-Y. Dong, X.-F.
Xu, J.-C. Mao, Org. Lett. 2015, 17, 5444.
Keywords: amidoselenation • amidotelluration • alkenes •
dioxygen • difunctionalization
11] K. Sun, X. Wang, Y.-H. Lv, G. Li, H.-Z. Jiao, C.-W. Dai, Y.-Y. Li, C. Zhang,
L. Liu, Chem. Commun. 2016, 52, 8471.
12] a) T. Punniyamurthy, S. Velusamy, J. Iqbal, Chem. Rev. 2005, 105, 2329;
b) A. E. Wendlandt, A. M. Suess, S. S. Stahl, Angew. Chem. 2011, 123,
[
1] a) R. Hili, A. K. Yudin, Nat. Chem. Biol. 2006, 2, 284; b) A. Ricci, Amino
Group Chemistry: From Synthesis to the Life Sciences, 1st ed.; Wiley-
VCH: Weinheim, 2007.
11256; Angew. Chem. Int. Ed. 2011, 50, 11062; c) Z. Shi, C. Zhang, C.
Tang, N. Jiao, Chem. Soc. Rev. 2012, 41, 3381; d) W. Wu, H. Jiang, S.
Adimurthy, Acc. Chem. Res. 2012, 45, 1736.
[
2] For selected reviews, see: a) J. F. Hartwig, Acc. Chem. Res. 2012, 45,
[
13] a) Q.-Q. Lu, J. Zhang, F.-L. Wei, Y. Qi, H.-M. Wang, Z.-L. Liu, A. Lei,
Angew. Chem. 2013, 125, 7297; Angew. Chem. Int. Ed. 2013, 52, 7156;
b) Q.-Q. Lu, J. Zhang, G.-L. Zhao, Y. Qi, H.-M. Wang, A. Lei, J. Am.
Chem. Soc. 2013, 135, 11481; c) W. Wei, C.-L. Liu, D.-D. Yang, J.-W.
Wen, J.-M. You, Y.-R. Suo, H. Wang, Chem. Commun. 2013, 49, 10239;
d) X. Sun, X.-Y. Li, S. Song, Y.-C. Zhu, Y.-F. Liang, N. Jiao, J. Am. Chem.
864; b) P. Mueller, C. Fruit, Chem. Rev. 2003, 103, 2905; c) A. R. Dick, M.
S. Sanford, Tetrahedron 2006, 62, 2439; d) H. M. L. Davies, M. S. Long,
Angew. Chem. 2005, 117, 3584; Angew. Chem. Int. Ed. 2005, 44, 3518;
e) H. M. L. Davies, J. R. Manning, Nature 2008, 451, 417; f) S. H. Cho, J.
Y. Kim, J. Y. Kwak, J. Kwak, S. Chang, Chem. Soc. Rev. 2011, 40, 5068;
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.