10.1002/adsc.202000578
Advanced Synthesis & Catalysis
[2] Y. Liu, L. Shen, M. Prashad, J. Tibbatts, O. Repič, T.
J. Blacklock, Org. Process Res. Dev. 2008, 12, 778-
780.
[3] a) H. Senboku, K. Nakahara, T. Fukuhara, S. Hara,
Tetrahedron Lett. 2010, 51, 435-438; b) V. Coeffard,
C. Thobie-Gautier, I. Beaudet, E. Le Grognec, J.-P.
Quintard, Eur. J. Org. Chem. 2008, 2008, 383-391; c)
E. R. Civitello, H. Rapoport, J. Org. Chem. 1992, 57,
834-840.
The p-toluenesulfonyl anion C eventually becomes p-
toluenesulfinic acid after combining with hydrogen
ions.[22a]
[4] R. R. Milburn, V. Snieckus, Angew. Chem. 2004, 116,
910-912; Angew. Chem. Int. Ed. 2004, 43, 892-894.
[5] a) H. S. Knowles, A. F. Parsons, R. M. Pettifer, S.
Rickling, Tetrahedron 2000, 56, 979-988; b) A. F.
Parsons, R. M. Pettifer, Tetrahedron Lett. 1996, 37,
1667-1670.
[6] S. K. Nayak, Synthesis 2000, 2000, 1575-1578.
[7] E. Vellemäe, O. Lebedev, U. Mäeorg, Tetrahedron
Lett. 2008, 49, 1373-1375.
Scheme 5. Proposed Reaction Mechanism.
[8] a) M. Sridhar, B. A. Kumar, R. Narender,
Tetrahedron Lett. 1998, 39, 2847-2850; b) B. Nyasse,
L. Grehn, U. Ragnarsson, Chem. Commun. 1997,
1017-1018.
[9] M. Uchiyama, Y. Matsumoto, S. Nakamura, T.
Ohwada, N. Kobayashi, N. Yamashita, A. Matsumiya,
T. Sakamoto, J. Am. Chem. Soc. 2004, 126, 8755-
8759.
In summary, we have successfully developed an
efficient and practical strategy for deprotecting tosyl
amides. The reaction is highlighted by its
chemoselectivity, affording reduced compounds in
high yields under mild reaction conditions. Further
development and application of photoactivated
reductive desulfonylation reactions and their
application to N-C bond formation are currently
underway.
[10] P. Nandi, M. Y. Redko, K. Petersen, J. L. Dye, M.
Lefenfeld, P. F. Vogt, J. E. Jackson, Org. Lett. 2008,
10, 5441-5444.
[11] G. Sabitha, B. V. S. Reddy, S. Abraham, J. S. Yadav,
Tetrahedron Lett. 1999, 40, 1569-1570.
Experimental Section
[12] a) G. Grach, J. Sopkova-de Oliveira Santos, J.-F.
Lohier, L. Mojovic, N. Plé, A. Turck, V. Reboul, P.
Metzner, J. Org. Chem. 2006, 71, 9572-9579; b) H.-F.
Duan, Y.-X. Jia, L.-X. Wang, Q.-L. Zhou, Org. Lett.
2006, 8, 2567-2569; c) M. Kuriyama, T. Soeta, X.
Hao, Q. Chen, K. Tomioka, J. Am. Chem. Soc. 2004,
126, 8128-8129; d) T. Hayashi, M. Kawai, N.
Tokunaga, Angew. Chem 2004, 116, 6251-6254;
Angew. Chem. Int. Ed. 2004, 43, 6125-6128; e) H.
Fujihara, K. Nagai, K. Tomioka, J. Am. Chem. Soc.
2000, 122, 12055-12056; f) D. A. Alonso, P. G.
Andersson, J. Org. Chem. 1998, 63, 9455-9461; g) T.
Ankner, G. Hilmersson, Org. Lett. 2009, 11, 503-506.
[13] T. Hamada, A. Nishida, O. Yonemitsu, J. Am. Chem.
Soc.1986, 108, 140-145.
[14] A. Yasuhara, M. Kameda, T. Sakamoto, Chem.
Pharm. Bull. 1999, 47, 809-812.
[15] T. Javorskis, E. Orentas, J. Org. Chem. 2017, 82,
13423-13439.
[16] F. Schoenebeck, J. A. Murphy, S.-z. Zhou, Y.
Uenoyama, Y. Miclo, T. Tuttle, J. Am. Chem. Soc.
2007, 129, 13368-13369.
[17] a) S. S. Hanson, E. Doni, K. T. Traboulsee, G.
Coulthard, J. A. Murphy, C. A. Dyker, Angew. Chem.
2015, 127, 11388-11391; Angew. Chem. Int. Ed. 2015,
54, 11236-11239; b) S. O'Sullivan, E. Doni, T. Tuttle,
J. A. Murphy, Angew. Chem. 2014, 126, 484-488;
Angew. Chem. Int. Ed. 2014, 53, 474-478.
To an 8 mL glass vial was added [Ir(ppy)2(dtbbpy)]PF6
(1.8 mg, 0.002 mmol), 1a (54.3 mg, 0.2 mmol), DIPEA
(265 uL, 1.6 mmol, 8.0 equiv), HCOOH (60 uL, 1.6 mmol,
8.0 equiv), and 2 mL of CH3CN. The mixture was then
evacuated and backfilled with Ar (3 times). The mixture
was then stirred rapidly and irradiated with a 5 W blue
LED (approximately 5 cm away from the light source) at
room temperature for 24 h. The reaction mixture was
concentrated in vacuum to remove the solvent. The
mixture was diluted with 10 mL H2O, and extracted with
EtOAc (3 × 8 mL). The combined organic extracts were
washed with brine (10 mL), dried over Na2SO4, and
concentrated in vacuo, purification was performed by flash
column chromatography on silica gel to afford the desired
product.
Acknowledgements
We are grateful to the National Natural Science Foundation of
China (21977056, 21732002, and 21672117) and the
Fundamental Research Funds for the Central Universities,
Nankai University (63191523) for generous financial support for
our programs.
References
[18] J. B. Edson, L. P. Spencer, J. M. Boncella, Org. Lett.
2011, 13, 6156-6159.
[1] S. Yoshida, K. Igawa, K. Tomooka, J. Am. Chem. Soc.
2012, 134, 19358-19361.
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