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In addition, diaryl sulfoximines could be effectively prepared
Communication
59, 2950; (b) J. M. Babcock, C. B. Gerwick, J. X. Huang, M. R. Loso,
G. Nakamura, C. P. Nolting, R. B. Rogers, T. C. Sparks, J. Thomas,
G. B. Watson and Y. Zhu, Pest Manage. Sci., 2011, 67, 328;
(c) G. B. Watson, M. R. Loso, J. M. Babcock, J. M. Hasler,
T. J. Letherer, C. D. Young, Y. Zhu, J. E. Casida and T. C. Sparks,
Insect Biochem. Mol. Biol., 2011, 41, 432.
5 (a) U. Lucking, G. Siemeister, P. Lienau, R. Jautelat and J. Schulze,
EP 2179991, 2010; (b) U. Lucking, R. Jautelat, M. Kruger, T. Brumby,
P. Lienau, M. Schafer, H. Briem, J. Schulze, A. Hillisch, A. Reichel
and G. Siemeister, ChemMedChem, 2013, 8, 1021.
6 S. J. Park, H. Baars, S. Mersmann, H. Buschmann, J. M. Baron,
P. M. Amann, K. Czaja, H. Hollert, K. Bluhm, R. Redelstein and
C. Bolm, ChemMedChem, 2013, 8, 217.
7 (a) H. R. Bentley and J. K. Whitehead, J. Chem. Soc., 1952, 1572;
(b) C. R. Johnson, M. Haake and C. W. Schroeck, J. Am. Chem. Soc.,
1970, 92, 6594; (c) P. Stoss and G. Satzinger, Angew. Chem., Int. Ed.,
1971, 10, 76; (d) C. R. Johnson and C. W. Schroeck, J. Am. Chem. Soc.,
1973, 95, 7418; (e) R. H. Rynbrandt and D. P. Balgoyen, J. Org. Chem.,
1978, 43, 1824; ( f ) J. Brandt and H.-J. Gais, Tetrahedron: Asymmetry,
1997, 8, 909.
8 (a) Y. Tamura, K. Sumoto, J. Minamikawa and M. Ikeda, Tetrahedron
Lett., 1972, 4137; (b) Y. Tamura, J. Minamikawa, K. Sumoto, S. Fujii
and M. Ikeda, J. Org. Chem., 1973, 38, 1239; (c) C. R. Johnson,
R. A. Kirchhoff and H. G. Corkins, J. Org. Chem., 1974, 39, 2458;
(d) S. Allenmark, S. Claeson and C. Lowendahl, Tetrahedron:
Asymmetry, 1996, 7, 361.
9 Cu-catalyzed: (a) J. F. K. Muller and P. Vogt, Tetrahedron Lett., 1998,
39, 4805; (b) H. Takada, K. Ohe and S. Uemura, Angew. Chem., Int. Ed.,
1999, 38, 1288; (c) C. Bolm, K. MuÇiz, N. Aguilar, M. Kesselgruber and
R. Raabe, Synthesis, 1999, 1251; (d) J. Nakayama, T. Otani, Y. Sugihara,
Y. Sano, A. Ishii and A. Sakamoto, Heteroat. Chem., 2001, 12, 333;
(e) E. Lacote, M. Amatore, L. Fensterbank and M. Malacria, Synlett,
2002, 116; ( f ) S. Cren, T. C. Kinahan, C. L. Skinner and H. Tye,
Tetrahedron Lett., 2002, 43, 2749; (g) C. S. Tomooka and E. M. Carreira,
HelV. Chim. Acta, 2003, 85, 3773; Rh-catalyzed: (h) H. Okamura and
C. Bolm, Org. Lett., 2004, 6, 1305; Ag-catalyzed: (i) G. Y. Cho and
C. Bolm, Org. Lett., 2005, 7, 4983; Fe-catalyzed: ( j) T. Bach and C. Korber,
Tetrahedron Lett., 1998, 39, 5015; (k) T. Bach and C. Kçrber, Eur. J. Org.
Chem., 1999, 1033; (l) O. Garcia Mancheno and C. Bolm, Org. Lett., 2006,
8, 2349; (m) O. Garcia Mancheno, J. Dallimore, A. Plant and C. Bolm,
Org. Lett., 2009, 11, 2429.
by this method from the corresponding sulfoxides (8r and 8s),
and we were pleased to find that both acyclic and cyclic dialkyl
sulfoxides were compatible with this reaction (8t and 8u).
Although the reaction mechanism of this transformation has
not been investigated, it is likely that a rhodium–nitrene species
is an intermediate based on prior literature reports.9h,10,11 Thus,
coordination of DPH to Rh2(esp)2, followed by loss of dinitro-
phenol, likely generates a reactive nitrene intermediate, which
then oxidizes the metal-coordinated sulfoxide to the corre-
sponding sulfoximine.
In summary, a novel, efficient, and safe method for the
preparation of free NH-sulfoximines has been developed via
rhodium-catalyzed imination of sulfoxides using O-(2,4-dinitro-
phenyl)hydroxylamine. This new approach features mild con-
ditions and good functional group tolerance, which should
permit its application to the synthesis of structurally complex
sulfoximines with agrochemical and clinical utility.1g
The authors gratefully acknowledge Indiana University
Purdue University Indianapolis for financial support. Funds
from an NSF-MRI award (CHE-0619254) were used to purchase
the Bruker 500 MHz NMR spectrometer used in this study.
Notes and references
1 For reviews on the synthesis and application of sulfoximines, see:
(a) C. R. Johnson, Aldrichimica Acta, 1985, 18, 3; (b) S. G. Pyne, Sulfur
Rep., 1992, 12, 57; (c) C. Worch, A. C. Mayer and C. Bolm, in
Organosulfur Chemistry in Asymmetric Synthesis, ed. T. Toru and
C. Bolm, Wiley-VCH, Weinheim, 2008, 209; (d) M. Reggelin and
C. Zur, Synthesis, 2000, 1; (e) F. Chemla, J. Chem. Soc., Perkin Trans. 1,
2002, 275; ( f ) H. Okamura and C. Bolm, Chem. Lett., 2004, 33, 482;
(g) U. Lucking, Angew. Chem., Int. Ed., 2013, 52, 9399; (h) V. Bizet,
R. Kowalczykb and C. Bolm, Chem. Soc. Rev., 2014, 43, 2426.
2 (a) H. Ikeuchi, Y.-M. Ahn, T. Otokawa, B. Watanabe, L. Hegazy,
J. Hiratake and N. G. J. Richards, Bioorg. Med. Chem., 2012, 20, 5915;
(b) J. A. Gutierrez, Y.-X. Pan, L. Koroniak, J. Hiratake, M. S. Kilberg
and N. G. J. Richards, Chem. Biol., 2006, 13, 1339; (c) H. Ikeuchi,
M. E. Meyer, Y. Ding, J. Hiratake and N. G. J. Richards, Bioorg. Med.
Chem., 2009, 17, 6641; (d) N. G. J. Richards and M. S. Kilberg, Annu.
Rev. Biochem., 2006, 75, 629.
10 J. L. Jat, M. P. Paudyal, H. Gao, Q.-L. Xu, M. Yousufuddin, D. Devarajan,
D. H. Ess, L. Ku¨rtis and J. R. Falck, Science, 2014, 343, 61.
11 For selected recent reviews on Rh-nitrene mediated reactions, see:
(a) P. Muller and C. Fruit, Chem. Rev., 2003, 103, 2905; (b) C. G.
Espino and J. Du Bois, in Modern Rhodium-Catalyzed Organic Reac-
tions, ed. P. A. Evans, Wiley-VCH, Weinheim, 2005, 379; (c) H. M. L.
Davies and J. R. Manning, Nature, 2008, 451, 417; (d) F. Collet, R. Dodd
and P. Dauban, Chem. Commun., 2009, 5061; (e) J. Du Bois, Org. Process
Res. Dev., 2011, 15, 758; ( f ) G. Dequirez, V. Pons and P. Dauban, Angew.
Chem., Int. Ed., 2012, 51, 7384; (g) M. M. Diaz-Requejo, A. Caballero,
M. R. Fructos and P. J. Perez, Catal. Met. Complexes, 2012, 38, 229;
(h) L. R. Jennifer, M. E. Harvey and J. Du Bois, Acc. Chem. Res., 2012,
45, 911.
3 P. Miller and G. W. L. James, Arch. Int. Pharmacodyn. Ther., 1978,
231, 328.
4 (a) Y. Zhu, M. R. Loso, G. B. Watscon, T. C. Sparks, R. B. Rogers,
J. X. Huang, B. C. Gerwick, J. M. Babcock, D. Kelley, V. B. Hedge,
B. M. Nugent, J. M. Renga, I. Denholm, K. Gorman, G. J. DeBoer,
J. Hasler, T. Meade and J. D. Thomas, J. Agric. Food Chem., 2011,
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