Organic Letters
Letter
Hasler, J.; Meade, T.; Thomas, J. D. J. Agric. Food Chem. 2011, 59,
Scheme 1. Plausible Mechanism
2950. (b) Medicinal chemistry: Lucking, U. Angew. Chem., Int. Ed.
̈
2013, 52, 9399.
(4) Johnson, C. R.; Rigau, J. J.; Haake, M.; McCants, D., Jr.; Keiser, J.
E.; Gertsema, A. Tetrahedron Lett. 1968, 3719.
(5) (a) Williams, T. R.; Booms, R. E.; Cram, D. J. J. Am. Chem. Soc.
1971, 93, 7338. (b) Schmidbaur, H.; Kammel, G. Chem. Ber. 1971,
104, 3234. (c) Johnson, C. R.; Schroeck, C. W.; Shanklin, J. R. J. Am.
Chem. Soc. 1973, 95, 7424. (d) For alkylations with trialkyloxonium
salts providing N-methyl and N-ethyl sulfoximines, see: Johnson, C. R.;
Haake, M.; Schroeck, C. W. J. Am. Chem. Soc. 1970, 92, 6594 and ref 4.
(6) (a) Furukawa, N.; Takahashi, F.; Yoshimura, T.; Morita, H.; Oae,
S. J. Chem. Soc., Perkin Trans. 2 1981, 432. (b) Raguse, B.; Ridley, D.
D. Aust. J. Chem. 1986, 39, 1665. (c) Johnson, C. R.; Lavergne, O. M. J.
Org. Chem. 1993, 58, 1922. (d) For alkylations with alkyl bromides in
KOH/DMSO mixtures, see: Hendriks, C. M. M.; Bohmann, R. A.;
Bohlem, M.; Bolm, C. Adv. Synth. Catal., accepted for publication;
DOI: 10.1002/adsc.201400193.
our hypothesis, diphenylmethane radical A was trapped by
TEMPO, and the yield of 3aa dropped to 15% (Scheme 2).
Scheme 2. Control Experiment
(7) (a) Bolm, C.; Bienewald, F.; Harms, K. Synlett 1996, 775.
(b) Bolm, C.; Hackenberger, C. P. R.; Simic,
D.; Bienewald, F. Synthesis 2002, 879.
́
O.; Verrucci, M.; Muller,
̈
(8) For reviews, see: (a) Li, C.-J.; Li, Z. Pure Appl. Chem. 2006, 78,
935. (b) Li, C.-J. Acc. Chem. Res. 2009, 42, 335. (c) Shi, W.; Liu, C.;
Lei, A. Chem. Soc. Rev. 2011, 40, 2761. (d) Liu, C.; Jin, L.; Lei, A.
Synlett 2010, 2527. (e) Scheuermann, C. J. Chem.Asian J. 2010, 5,
436. (f) Dong, V. M.; Yeung, C. S. Chem. Rev. 2011, 111, 1215.
(9) (a) Jiang, H.; Lin, A.; Zhu, C.; Cheng, Y. Chem. Commun. 2013,
49, 819. (b) Bian, Y.-J.; Chen, C.-Y.; Huang, Z.-Z. Chem.Eur. J.
2013, 19, 1129. (c) Zhang, T.; Bao, W. J. Org. Chem. 2013, 78, 1317.
(d) Ghosh, S. C.; Ngiam, J. S. Y.; Seayad, A. M.; Tuan, D. T.; Chai, C.
L. L.; Chen, A. J. Org. Chem. 2012, 77, 8007. (e) Cho, S. H.; Yoon, J.;
Chang, S. J. Am. Chem. Soc. 2011, 133, 5996. (f) John, A.; Nicholas, K.
M. J. Org. Chem. 2011, 76, 4158. (g) Shuai, Q.; Deng, G.; Chua, Z.;
Bohle, D. S.; Li, C.-J. Adv. Synth. Catal. 2010, 352, 632. (h) Monguchi,
D.; Fujiwara, T.; Furukawa, H.; Mori, A. Org. Lett. 2009, 11, 1607.
(i) Wang, L.; Fu, H.; Jiang, Y.; Zhao, Y. Chem.Eur. J. 2008, 14,
10722. (j) Brasche, G.; Buchwald, S. L. Angew. Chem., Int. Ed. 2008,
47, 1932. (k) Thu, H.-Y.; Yu, W.-Y.; Che, C.-M. J. Am. Chem. Soc.
2006, 128, 9048. (l) Uemura, T.; Imoto, S.; Chatani, N. Chem. Lett.
2006, 35, 842. (m) Chen, X.; Hao, X. S.; Goodhue, C. E.; Yu, J. Q. J.
Am. Chem. Soc. 2006, 128, 6790.
In summary, we developed iron-catalyzed hetero-cross-
dehydrogenative coupling reactions for N-alkylations of N-H
sulfoximines with diarylmethanes. The transformation provides
a new strategy for the synthesis of N-alkylated sulfoximines with
α-branched substituents, which are otherwise difficult to
prepare. Further studies along those lines are in progress.
ASSOCIATED CONTENT
* Supporting Information
■
S
General experimental procedure and characterization details.
This material is available free of charge via the Internet at
AUTHOR INFORMATION
Corresponding Author
■
(10) (a) Pelletier, G.; Powell, D. A. Org. Lett. 2006, 8, 6031.
(b) Powell, D. A.; Fan, H. J. Org. Chem. 2010, 75, 2726.
(11) (a) Zhang, Y.; Fu, H.; Jiang, Y.; Zhao, Y. Org. Lett. 2007, 9,
3813. (b) Liu, X.; Zhang, Y.; Wang, L.; Fu, H.; Jiang, Y.; Zhao, Y. J.
Org. Chem. 2008, 73, 6207.
Notes
The authors declare no competing financial interest.
(12) Wang, Z.; Zhang, Y.; Fu, H.; Jiang, Y.; Zhao, Y. Org. Lett. 2008,
10, 1863.
ACKNOWLEDGMENTS
■
(13) Pan, S.; Liu, J.; Li, H.; Wang, Z.; Guo, X.; Li, Z. Org. Lett. 2010,
12, 1932 and references therein.
(14) For the use of a cobalt catalyst in such couplings, see: Ye, Y.-H.;
Zhang, J.; Wang, G.; Chen, S.-Y.; Yu, X.-Q. Tetrahedron 2011, 67,
4649.
(15) (a) Miyasaka, M.; Hirano, K.; Satah, T.; Kowalczyk, R.; Bolm,
C.; Miura, M. Org. Lett. 2011, 13, 359. (b) Wang, L.; Priebbenow, D.
L.; Zou, L.-H.; Bolm, C. Adv. Synth. Catal. 2013, 355, 1490. (c) Wang,
L.; Huang, H.; Priebbenow, D. L.; Pan, F.-F.; Bolm, C. Angew. Chem.,
Int. Ed. 2013, 52, 3478. (d) See also: Priebbenow, D. L.; Becker, P.;
Bolm, C. Org. Lett. 2013, 15, 6155.
(16) Attempts to use diethyl malonate, ethyl 3-oxobutanoate,
xanthene, fluorene, indane, triphenyl methane, ethyl benzene, or
toluene as the substrate instead of diarylmethanes remained
unsuccessful.
Y.C. and W.D. thank the China Scholarship Council for
predoctoral stipends. K.P. is grateful to the Alexander von
Humboldt Foundation for a postdoctoral fellowship.
REFERENCES
■
(1) Bentley, H. R.; McDermott, E. E.; Pace, J.; Whitehead, J. K.;
Moran, T. Nature 1950, 165, 150.
(2) For reviews on sulfoximines, see: (a) Johnson, C. R. Acc. Chem.
Res. 1973, 6, 341. (b) Reggelin, M.; Zur, C. Synthesis 2000, 1.
(c) Harmata, M. Chemtracts 2003, 16, 660. (d) Gais, H.-J. Heteroat.
Chem. 2007, 18, 472. (e) Okamura, H.; Bolm, C. Chem. Lett. 2004, 33,
482. (f) Bolm, C. In Asymmetric Synthesis with Chemical and Biological
Methods; Enders, D., Jaeger, K.-E., Eds.; Wiley-VCH: Weinheim, 2007;
p 149. (g) Worch, C.; Mayer, A. C.; Bolm, C. In Organosulfur
Chemistry in Asymmetric Synthesis; Toru, T., Bolm, C., Eds.; Wiley-
VCH: Weinheim, 2008; p 209. (h) Bizet, V.; Kowalczyk, R.; Bolm, C.
Chem. Soc. Rev. 2014, 43, 2426.
(17) Wei, W.-T.; Zhou, M.-B.; Fan, J.-H.; Liu, W.; Song, R.-J.; Liu, Y.;
Hu, M.; Xie, P.; Li, J.-H. Angew. Chem., Int. Ed. 2013, 52, 3638 and
references therein.
(18) (a) Li, Z.; Cao, L.; Li, C.-J. Angew. Chem., Int. Ed. 2007, 46,
6505. (b) Li, Y.-Z.; Li, B.-J.; Lu, X.-Y.; Lin, S.; Shi, Z.-J. Angew. Chem.,
Int. Ed. 2009, 48, 3817.
(3) For two recent relevant examples, see: (a) Crop protection:
Zhu, Y.; Loso, M. R.; Watson, G. B.; Sparks, T. C.; Rogers, R. B.;
Huang, J. X.; Gerwick, B. C.; Babcock, J. M.; Kelley, D.; Hegde, V. B.;
Nugent, B. M.; Renga, J. M.; Denholm, I.; Gorman, K.; DeBoer, G. J.;
2002
dx.doi.org/10.1021/ol500573f | Org. Lett. 2014, 16, 2000−2002