Sulfoxide-to-Sulfilimine Conversions: Use of Modified Burgess-Type Reagents
moved under reduced pressure to afford the product in high
purity.
125, 9570–9580; Angew. Chem. Int. Ed. 2013, 52, 9399–
9408.
[7] a) S. J. Park, H. Baars, S. Mersmann, H. Buschmann,
J. M. Baron, P. M. Amann, K. Czaja, H. Hollert, K.
Bluhm, R. Redelstein, C. Bolm, ChemMedChem 2013,
8, 217–220; b) X. Y. Chen, S. J. Park, H. Buschmann,
M. De Rosa, C. Bolm, Bioorg. Med. Chem. Lett. 2012,
22, 4307–4309; c) X. Y. Chen, H. Buschmann, C. Bolm,
Synlett 2012, 23, 2808–2810; d) S. J. Park, H. Busch-
mann, C. Bolm, Bioorg. Med. Chem. Lett. 2011, 21,
4888–4890.
Acknowledgements
We thank Dr. Iuliana Atodiresei and Marina Bohlem (both
RWTH Aachen University) for the X-ray crystallographic
analysis and various synthetic contributions, respectively. The
proof-reading of the manuscript by Dr. Daniel Priebbenow
(RWTH Aachen University) is appreciated.
[8] a) J. K. Whitehead, H. R. Bentley, J. Chem. Soc. 1952,
1572–1574; b) R. Fusco, F. Tericoni, Chim. Ind. (Milan)
1965, 47, 61–62; c) C. R. Johnson, M. Haake, C. W.
Schrock, J. Am. Chem. Soc. 1970, 92, 6594–6598;
d) R. H. Rynbrandt, D. P. Balgoyen, J. Org. Chem.
1978, 43, 1824–1825; e) for a recent industrial applica-
tion of this method (on a 0.034 mol scale) in the syn-
thesis of a factor Xa inhibitor, see: V. Pandya, M. Jain,
G. Chakrabarti, H. Soni, B. Parmar, B. Chaugule, J.
Patel, T. Jarag, J. Joshi, N. Joshi, A. Rath, V. Unadkat,
B. Sharma, H. Ajani, J. Kumar, K. V. V. M. Sairam, H.
Patel, P. Patel, Eur. J. Med. Chem. 2012, 58, 136–152.
[9] a) Y. Tamura, K. Sumoto, J. Minamikawa, M. Ikeda,
Tetrahedron Lett. 1972, 4137–4140; b) C. R. Johnson,
R. A. Kirchoff, H. G. Corkins, J. Org. Chem. 1974, 39,
2458–2459; c) for studies on the stability of MSH, see:
J. Mendiola, J. A. Rincꢃn, C. Mateos, J. F. Soriano, ꢄ.
de Frutos, J. K. Niemeier, E. M. Davis, Org. Process
Res. Dev. 2009, 13, 263–267.
[10] a) For a comparative study of metal-catalyzed imina-
tions and deprotection protocols, see: O. Garcꢅa Man-
cheÇo, C. Bolm, Chem. Eur. J. 2007, 13, 6674–6681;
b) for an alternative electrochemical method, see: T.
Siu, A. K. Yudin, Org. Lett. 2002, 4, 1839–1842.
[11] a) O. Garcꢅa MancheÇo, O. Bistri, C. Bolm, Org. Lett.
2007, 9, 3809–3811; b) O. Garcꢅa MancheÇo, C. Bolm,
Org. Lett. 2007, 9, 2951–2954; c) A. Pandey, C. Bolm,
Synthesis 2010, 2922–2925.
References
[1] a) C. R. Johnson, Acc. Chem. Res. 1973, 6, 341–347;
b) M. Reggelin, C. Zur, Synthesis 2000, 1–64; c) C.
Worch, A. C. Mayer, C. Bolm, in: Organosulfur
Chemistry in Asymmetric Synthesis. (Eds.: T. Toru, C.
Bolm), Wiley-VCH, Weinheim, 2008, pp 209–229; d) R.
Bentley, Chem. Soc. Rev. 2005, 34, 609–624; e) H.-J.
Gais, Heteroat. Chem. 2007, 18, 472–481.
[2] a) M. Harmata, Chemtracts 2003, 16, 660–666; b) H.
Okamura, C. Bolm, Chem. Lett. 2004, 33, 482–487;
c) C. Bolm, in: Asymmetric Synthesis with Chemical
and Biological Methods, (Eds.: D. Enders, K.-E.
Jaeger), Wiley-VCH, Weinheim, 2007, pp 149–176;
d) C. Bolm, Latv. J. Chem. 2012, 49–50.
[3] a) H. R. Bentley, E. E. McDermott, J. K. Whitehead,
Nature 1950, 165, 735; b) H. R. Bentley, E. E. McDer-
mott, J. Pace, J. K. Whitehead, T. Moran, Nature 1950,
165, 150–151; c) H. R. Bentley, E. E. McDermott, J.
Pace, J. K. Whitehead, T. Moran, Nature 1949, 163,
675–676.
[4] a) Y. Zhu, M. R. Loso, G. B. Watson, T. C. Sparks, R. B.
Rogers, J. X. Huang, B. C. Gerwick, J. M. Babcock, D.
Kelley, V. B. Hegde, B. M. Nugent, J. M. Renga, I. Den-
holm, K. Gorman, G. J. DeBoer, J. Hasler, T. Meade,
J. D. Thomas, J. Agric. Food Chem. 2011, 59, 2950–
2957; b) J. M. Babcock, C. B. Gerwick, J. X. Huang,
M. R. Loso, G. Nakamura, S. P. Nolting, R. B. Rogers,
T. C. Sparks, J. Thomas, G. B. Watson, Y. Zhu, Pest.
Manag. Sci. 2011, 67, 328–334; c) G. B. Watson, M. R.
Loso, J. M. Babcock, J. M. Hasler, T. J. Letherer, C. D.
Young, Y. Zhu, J. E. Casida, T. C. Sparks, Insect. Bio-
chem. Mol. Biol. 2011, 41, 432–439; d) T. C. Sparks,
M. R. Loso, G. B. Watson, J. M. Babcock, V. J. Kramer,
Y. Zhu, B. M. Nugent, J. D. Thomas, in: Modern Crop
Protection Compounds, 2nd edn., Vol. 3, (Eds.: W.
Kraemer, U. Schirmer, P. Jeschke, M. Witschel), Wiley-
VCH, Weinheim, 2012, pp 1226–1237.
[5] a) U. Lꢂcking, R. Jautelat, M. Krueger, T. Brumby, P.
Lienau, M. Schaefer, H. Briem, J. Schulze, A. Hillisch,
A. Reichel, A. M. Wengner, G. Siemeister, ChemMed-
Chem 2013, 8, 1067–1085; b) G. Siemeister, U. Lꢂcking,
A. M. Wengner, P. Lienau, W. Steinke, C. Schatz, D.
Mumberg, K. Ziegelbauer, Mol. Cancer Ther. 2012, 11,
2265–2273; c) J. Krueger, J. Gries, K. Lovis, J. Hassfeld,
WO Patent WO-A1 038411, 2012.
[12] a) N-Cyanosulfoximines such as Sulfoxaflor (1) can
also be prepared by cyanations of NH-sulfoximines
with cyanogen bromide (BrCN). For a recent industrial
application of this method, see: C. Gnamm, A. Jean-
guenat, A. C. Dutton, C. Grimm, D. P. Kloer, A. J.
Crossthwaite, Bioorg. Med. Chem. Lett. 2012, 22, 3800–
3806. For analogous cyanation reactions with sulfondi-
AHCTUNGTREGiNNUN mines, see: b) R. Appel, G. Vollmer, Chem. Ber. 1970,
103, 2555–2561; c) M. Candy, C. Guyon, S. Mersmann,
J.-R. Chen, C. Bolm, Angew. Chem. 2012, 124, 4516–
4519; Angew. Chem. Int. Ed. 2012, 51, 4440–4443.
[13] S. Raghavan, S. Mustafa, K. Rathore, Tetrahedron Lett.
2008, 49, 4256–4259.
[14] Burgess reagents are inner salts of (alkoxycarbonylsulf-
AHCTUNGTREGaNNUN moyl)triethylammonium hydroxides, which are often
used for mild dehydrations or other functional group
transformations. For the initial discovery, see: a) G. M.
Atkins, E. M. Burgess, J. Am. Chem. Soc. 1968, 90,
4744–4745; b) E. M. Burgess, H. R. Penton, E. A.
Taylor, J. Am. Chem. Soc. 1970, 92, 5224–5226.
[15] For selected reviews on applications of Burgess re-
agents, see: a) S. Santra, Synlett 2009, 328–329; b) S.
Khapli, S. Dey, D. Mal, J. Indian Inst. Sci. 2001, 81,
[6] For a recent overview on the use of sulfoximines in me-
dicinal chemistry, see: U. Lꢂcking, Angew. Chem. 2013,
Adv. Synth. Catal. 0000, 000, 0 – 0
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