Organic Letters
Letter
(e) Gnanamgari, D.; Sauer, E. L. O.; Schley, N. D.; Butler, C.;
Incarvito, C. D.; Crabtree, R. H. Organometallics 2009, 28, 321.
(f) Michlik, S.; Kempe, R. Chem.Eur. J. 2010, 16, 13193. (g) Zhu,
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(4) For selected examples, see: (a) Corma, A.; Rodenas, T.; Sabater,
M. J. Chem.Eur. J. 2010, 16, 254. (b) He, W.; Wang, L.; Sun, C.;
Wu, K.; He, S.; Chen, J.; Wu, P.; Yu, Z. Chem.Eur. J. 2011, 17,
13308. (c) Dang, T. T.; Ramalingam, B.; Shan, S. P.; Seayad, A. M.
ACS Catal. 2013, 3, 2536.
(5) (a) Li, F.; Shan, H.; Kang, Q.; Chen, L. Chem. Commun. 2011, 47,
5058. (b) Li, F.; Shan, H.; Chen, L.; Kang, Q.; Zou, P. Chem. Commun.
2012, 48, 603. (c) Li, F.; Sun, C.; Shan, H.; Zou, X.; Xie, J.
ChemCatChem 2013, 5, 1543. (d) Li, F.; Qu, P.; Ma, J.; Zou, X.; Sun,
C. ChemCatChem 2013, 5, 2178. (e) Sun, C.; Zou, X.; Li, F. Chem.
Eur. J. 2013, 19, 14030. (f) Qu, P.; Sun, C.; Ma, J.; Li, F. Adv. Synth.
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10447.
Scheme 6. Synthesis of Biologically Active Molecule
product in 80% yield. The new route exhibited obvious
advantages over the previous multistep synthesis of C-
7280948.6a
In summary, we have demonstrated a simple, highly efficient,
and general strategy for direct synthesis of amino-(N-
alkyl)benzenesulfonamides via iridium-catalyzed N-alkylation
of aminobenzenesulfonamides bearing both different types of
amino groups with alcohols as alkylating agents. Notably, this
research exhibited the potential for the recognition of different
types of amino groups in the N-alkylation of complex molecules
with alcohols, facilitating the progress of the transition-metal-
catalyzed “hydrogen autotransfer (or hydrogen-borrowing)
process”.
(6) For selected examples, see: (a) Bissinger, E. M.; Heinke, R.;
Spannhoff, A.; Eberlin, A.; Metzger, E.; Cura, V.; Hassenboehler, P.;
ASSOCIATED CONTENT
* Supporting Information
Experimental procedures, characterization data, and a CIF file
giving crystallographic data for product 3ag. The Supporting
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S
Cavarelli, J.; Schule, R.; Bedford, M. T.; Sippl, W.; Jung, M. Bioorg.
̈
Med. Chem. 2011, 19, 3717. (b) Ghosh, A. K.; Chapsal, B. D.; Parham,
G. L.; Steffey, M.; Agniswamy, J.; Wang, Y.; Amano, M.; Weber, I. T.;
Mitsuya, H. J. Med. Chem. 2011, 54, 5890. (c) Agniswamy, J.; Shen, C.;
Wang, Y.; Ghosh, A. K.; Rao, K. V.; Xu, C.; Sayer, J. M.; Louis, J. M.;
Weber, I. T. J. Med. Chem. 2013, 56, 4017. (d) Ghosh, A. K.; Parham,
G. L.; Martyr, C. D.; Nyalapatla, P. R.; Osswald, H. L.; Agniswamy, J.;
Wang, Y.; Amano, M.; Weber, I. T.; Mitsuya, H. J. Med. Chem. 2013,
56, 6792.
AUTHOR INFORMATION
Corresponding Author
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Notes
(7) For selected examples about the N-alkylation of sulfonamides
with alcohols using other transition metal catalysts, see: (a) Shi, F.;
Tse, M. K.; Zhou, S.; Pohl, M. M.; Radnik, J.; Hubner, S.; Jahnisch, K.;
̈
̈
The authors declare no competing financial interest.
Bruckner, A.; Beller, M. J. Am. Chem. Soc. 2009, 131, 1775. (b) Shi, F.;
̈
Tse, M. K.; Cui, X.; Gordes, D.; Michalik, D.; Thurow, K.; Deng, Y.;
̈
ACKNOWLEDGMENTS
Beller, M. Angew. Chem., Int. Ed. 2009, 48, 5912.
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(8) Fujita, Yamaguchi and co-workers reported the oxidation of
alcohols via hydrogen transfer (Oppenauer-type oxidation) catalyzed
by [Cp*IrCl2]2; see: Fujita, K.; Furukawa, S.; Yamaguchi, R. J.
Organomet. Chem. 2002, 649, 289.
Financial support by National Natural Science Foundation of
China (21272115) and the State Key Laboratory of Fine
Chemicals (KF1401) is greatly appreciated.
(9) Bergman and co-workers demonstrated the amido−alkoxo
exchange reaction for Cp*Ir complexes; see: Glueck, D. S.;
Winslow, L. J. N.; Bergman, R. G. Organometallics 1991, 10, 1462.
(10) It was reported that reactions of [Cp*IrCl2]2 with an arylamine
or arylsulfonamide in the presence of a base lead to the formation of
dinuclear iridium complexes; see: (a) Dobbs, D. A.; Bergman, R. G.
Organometallics 1994, 13, 4594. (b) Ishiwata, K.; Kuwata, S.; Ikariya,
T. Organometallics 2006, 25, 5847.
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