3-Oxo-1,3λ⁶,4-oxathiazines: A Novel Class of Heterocyclic S,O-Acetals

Dedicated to Prof. D. Enders on the occasion of his 70^th birthday

Abstract

In this study, two synthetic methods for the synthesis of a hitherto unknown class of heterocyclic diastereo- and enantiopure S,O-acetals are described. Method A involves a chemoselective monohalogenation of sulfoximines and method B a stereoselective ring opening of sulfonimidates with a carbenoid as the key step, both followed by a base-induced cyclization of the S-(halomethyl)sulfoximine intermediates. The absolute configuration of the resulting 3-oxo-1,3λ⁶,4-oxathiazines has been confirmed by X-ray structural analysis. Furthermore, the first experiments exploring the reactivity of the new compounds are described.

Key words

sulfoximines - sulfonimidates - oxathiazines - carbenoids - umpolung

• References

• 1a Reggelin M, Slavik S, Bühle P. Org. Lett. 2008; 10: 4081
• 1b Reggelin M, Junker B, Heinrich T, Slavik S, Bühle P. J. Am. Chem. Soc. 2006; 128: 4023
• 1c Reggelin M, Zur C. Synthesis 2000; 1
• 1d Reggelin M, Gerlach M, Vogt M. Eur. J. Org. Chem. 1999; 1011
• 1e Reggelin M, Heinrich T. Angew. Chem. Int. Ed. 1998; 37: 2883
• 1f Reggelin M, Weinberger H, Gerlach M, Welcker R. J. Am. Chem. Soc. 1996; 118: 4765
• 1g Reggelin M, Weinberger H. Angew. Chem. Int. Ed. 1994; 33: 444
• 1h Reggelin M, Kühl J, Kaiser JP, Bühle P. Synthesis 2006; 2224
• 2a Köhler A, Raabe G, Runsink J, Kohler F, Gais HJ. Eur. J. Org. Chem. 2014; 3355
• 2b Acikalin S, Raabe G, Runsink J, Gais HJ. Eur. J. Org. Chem. 2011; 5991
• 2c Gais HJ. Heteroat. Chem. 2007; 18: 472
• 2d Gais HJ, Bruns PR, Raabe G, Hainz R, Schleusner M, Runsink J, Babu GS. J. Am. Chem. Soc. 2005; 127: 6617
• 3a Reggelin M, Junker B. Chem. Eur. J. 2001; 7: 1232
• 3b Reggelin M, Welcker R. Tetrahedron Lett. 1995; 36: 5885
• 3c Reggelin M, Weinberger H. Tetrahedron Lett. 1992; 33: 6959
• 4a Bosshammer S, Gais HJ. Synlett 1998; 99
• 4b Imamoto T, Koto H. Synthesis 1985; 982
• 5 CCDC 617316 (8a), CCDC 617318 (8b) and CCDC 617315 (16b) contain the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
• 6 The terms S _X and R _X are descriptors used to describe the sense of chirality (S or R) at heteroatom positions (X). Cram DJ. J. Am. Chem. Soc. 1970; 92: 7369
• 7 Sadhu KM, Matteson DS. Tetrahedron Lett. 1986; 27: 795