A Practical Approach to N-(Trifluoroacetyl)sulfilimines

Abstract

A new, simple method for the synthesis of N-(trifluoroacetyl)-protected sulfilimines from sulfides by a transition-metal-free, one-pot protocol is presented. The salient features of this process include the use of low-cost 1,3-dibromo-5,5-dimethylhydantoin, mild reaction conditions, and a broad substrate scope. The safety and robustness of the method has also been demonstrated by operations on a kilogram scale. In addition, a chiral resolution of a corresponding sulfoximine was achieved on a large scale.

Key words

N-(trifluoroacetyl)sulfilimines - sulfilimines - sulfox­imines - chiral resolution

• References and Notes


See, for instance:
• 1a Okamura H, Bolm C. Chem. Lett. 2004; 33: 482
• 1b Reggelin M, Zur C. Synthesis 2000; 1
• 1c Gais H.-J. Heteroat. Chem. 2007; 18: 472
• 1d Frings M, Atodiresei I, Wang Y, Runsink J, Raabe G, Bolm C. Chem. Eur. J. 2010; 16: 4577 ; and references cited therein
• 2a Kahraman M, Sinishtaj S, Dolan PM, Kensler TW, Peleg S, Saha U, Chuang SS, Berstein G, Korczak B, Posner GH. J. Med. Chem. 2004; 47: 6854
• 2b Raza A, Sham YY, Vince R. Bioorg. Med. Chem. Lett. 2008; 18: 5406
• 2c Walker DP, Zawistoski MP, McGlynn MA, Li J.-C, Kung DW, Bonnette PC, Baumann A, Buckbinder L, Houser JA, Boer J, Mistry A, Han S, Xing L, Guzman-Perez A. Bioorg. Med. Chem. Lett. 2009; 19: 3253
• 2d Luecking U, Siemeister G, Lienau P, Jautelat R, Schulze J. EP 2179991, 2010
• 2e Lücking U, Jautelat R, Krüger M, Brumby T, Lienau P, Schäfer M, Briem H, Schulze J, Hillisch A, Reichel A, Wengner AM, Siemeister G. ChemMedChem 2013; 8: 1067
• 2f Lücking U. Angew. Chem. Int. Ed. 2013; 52: 9399
• 3 Bentley HR, Whitehead JK. J. Chem. Soc. 1952; 1572
• 4 Tamura Y, Sumoto K, Minamikawa J, Ikeda M. Tetrahedron Lett. 1972; 4137
• 5 Mendiola J, Rincón JA, Mateos C, Soriano JF, de Frutos O, Niemeier JK, Davis EM. Org. Process Res. Dev. 2009; 13: 263
• 6 Cho GY, Bolm C. Tetrahedron Lett. 2005; 46: 8007
• 7 Siu T, Yudin AK. Org. Lett. 2002; 4: 1839

For an overview, see:
• 8a Mancheno OG, Bolm C. Chem. Eur. J. 2007; 13: 6674
• 8b Barry N, Brondel N, Lawrence SE, Maguire AR. Tetrahedron 2009; 65: 10660
• 9a Bach T, Körber C. Eur. J. Org. Chem. 1999; 1033
• 9b Mancheno OG, Bolm C. Org. Lett. 2006; 8: 2349
• 9c Mancheno OG, Dallimore J, Plant A, Bolm C. Org. Lett. 2009; 11: 2429
• 10 Cho GY, Bolm C. Org. Lett. 2005; 7: 4983
• 11a Nakayama J, Otani T, Sugihara Y, Sano Y, Ishii A, Sakamoto A. Heteroat. Chem. 2001; 12: 333
• 11b Cren S, Kinahan TC, Skinner CL, Tye H. Tetrahedron Lett. 2002; 43: 2749
• 11c Lacote E, Amatore M, Fensterbank L, Malacria M. Synlett 2002; 116
• 12a Okamura H, Bolm C. Org. Lett. 2004; 6: 1305
• 12b Collet F, Dodd RH, Dauban P. Org. Lett. 2008; 10: 5473
• 13 Bizet V, Buglioni L, Bolm C. Angew. Chem. Int. Ed. 2014; 53: 5639
• 14 Tomooka CS, LeCloux DD, Sasaki H, Carreira EM. Org. Lett. 1999; 1: 149
• 15 Ochiai M, Naito M, Miyamoto K, Hayashi S, Nakanishi W. Chem. Eur. J. 2010; 16: 8713
• 16a Mancheno OG, Bistri O, Bolm C. Org. Lett. 2007; 9: 3809
• 16b Pandey A, Bolm C. Synthesis 2010; 2922
• 17 Luecking U, Krueger M, Jautelat R, Siemeister G. WO 2005037800, 2005
• 18 Calorimetric measurements revealed that THF solutions of DBDMH have a limited stability at 20 °C and should therefore be handled at 2–8 °C. Solutions of DBDMH in, for example, 1,4-dioxane are more robust and can be used as an alternative without a detrimental effect on quality or yield.
• 19 General Experimental Procedure for the Formation of N-(Trifluoroacetyl)-Protected Sulfilimines on a Laboratory Scale In an inert gas atmosphere, a mixture of the sulfide (34.7 mmol) and trifluoroacetamide (5.89 g, 52.1 mmol) in THF (20 mL) was added under ice cooling within 45 min to a suspension of NaH (60% in mineral oil; 1.25 g, 31.3 mmol) in THF (25 mL). Then, a freshly prepared solution of 1,3-dibromo-5,5-dimethylhydantoin (14.9 g, 52.1 mmol) in THF (37 mL) was added within 60 min at 20 °C. The mixture was stirred for 3 h; the reaction was quenched with 10% aq citric acid solution (35 mL), and toluene (70 mL) was added. The organic layer was washed with 25% aq sodium sulfite solution (35 mL) and water (3 × 40 mL). The solvent was removed by distillation, and the residue was purified by silica gel chromatography (EtOAc–n-heptane = 1:1).
• 20a Tomooka CS, Carreira EM. Helv. Chim. Acta 2002; 85: 3773
• 20b Wang J, Frings M, Bolm C. Angew. Chem. Int. Ed. 2013; 52: 8661
• 20c Wang J, Frings M, Bolm C. Chem. Eur. J. 2014; 20: 966
• 21a Johnson CR, Kirchhoff RA, Corkins HG. J. Org. Chem. 1974; 39: 2458
• 21b Pandey AG, McGrath MJ, Mancheno OG, Bolm C. Synthesis 2011; 3827
• 22a Fusco R, Tericoni F. Chem. Ind. 1965; 47: 61
• 22b Johnson CR, Schroeck CW. J. Am. Chem. Soc. 1973; 95: 7418
• 22c Johnson CR, Schroeck CW, Shanklin JR. J. Am. Chem. Soc. 1973; 95: 7424
• 22d Shiner CS, Berks AH. J. Org. Chem. 1988; 53: 5542
• 22e Brandt J, Gais HJ. Tetrahedron: Asymmetry 1997; 8: 909
• 23 S-Oxidations with Oxone® leading to sulfones and sulfoxides are well documented; see, for instance: Trost BM, Curran DP. Tetrahedron Lett. 1981; 22: 1287