Synthesis, Table of Contents Synthesis 2015; 47(13): 1951-1959DOI: 10.1055/s-0034-1380536 paper © Georg Thieme Verlag Stuttgart · New YorkDirect Access to N-Alkylsulfoximines from Sulfides by a Sequential Imidation/Oxidation Procedure Authors Author Affiliations Carl Albrecht Dannenberg Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany Email: carsten.bolm@oc.rwth-aachen.de Vincent Bizet* Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany Email: carsten.bolm@oc.rwth-aachen.de Carsten Bolm* Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany Email: carsten.bolm@oc.rwth-aachen.de Recommend Article Abstract Buy Article(opens in new window) All articles of this category(opens in new window) Abstract Synthetically relevant N-alkyl-substituted sulfoximines are directly prepared from sulfides by an unprecedented one-pot imidation/oxidation sequence. In situ generated N-bromoalkylamines serve as readily accessible imidating agents leading to N-alkylsulfiliminium bromides that are subsequently oxidized providing the corresponding N-alkylsulfoximines. In this manner, gram quantities of the products can be obtained in a short period of time avoiding the use of toxic and cumbersome to handle alkylating reagents. Key words Key wordssulfoximine - imidation - oxidation - synthetic method - sulfide Full Text References References For reviews about sulfoximines, see: 1a Reggelin M, Zur C. Synthesis 2000; 1 1b Harmata M. Chemtracts 2003; 16: 660 1c Okamura H, Bolm C. Chem. Lett. 2004; 33: 482 1d Bolm C In Asymmetric Synthesis with Chemical and Biological Methods . Enders D, Jaeger K.-E. Wiley-VCH; Weinheim: 2007: 149 1e Gais H.-J. Heteroat. Chem. 2007; 18: 472 1f Bolm C. Latv. J. Chem. 2012; 49 1g Bizet V, Kowalczyk R, Bolm C. Chem. Soc. Rev. 2014; 43: 2426 1h Shen X, Hu J. Eur. J. Org. Chem. 2014; 4437 For recent articles dealing with sulfoximine syntheses, see: 2a Wang J, Frings M, Bolm C. Angew. Chem. Int. Ed. 2013; 52: 8661 ; Angew. Chem. 2013, 125, 8823 2b Wang J, Frings M, Bolm C. Chem. Eur. J. 2014; 20: 966 2c Bizet V, Buglioni L, Bolm C. Angew. Chem. Int. Ed. 2014; 53: 5639 ; Angew. Chem. 2014, 126, 5745 2d Buglioni L, Bizet V, Bolm C. Adv. Synth. Catal. 2014; 356: 2209 2e Miao J, Richards NG. J, Ge H. Chem. Commun. 2014; 50: 9687 ; and references cited therein 3 For a recent overview about the use of sulfoximines in medicinal chemistry, see: Lücking U. Angew. Chem. Int. Ed. 2013; 52: 9399 ; Angew. Chem. 2013, 125, 9570 4a Lücking U, Jautelat R, Krueger M, Brumby T, Lienau P, Schaefer M, Briem H, Schulze J, Hillisch A, Reichel A, Wengner AM, Siemeister G. ChemMedChem 2013; 8: 1067 4b Siemeister G, Lücking U, Wengner AM, Lienau P, Steinke W, Schatz C, Mumberg D, Ziegelbauer K. Mol. Cancer Ther. 2012; 11: 2265 4c Krüger J, Gries J, Lovis K, Hassfeld J. Bayer Pharma AG, Patent WO 2012/038411 A1, 2012 4d Foote KM, Nissink JW. M, Turner P AstraZeneca Patent WO 2011/154737 A1, 2011 For bioactivities of N-methylated sulfoximines, see: 5a 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 5b Park SJ, Baars H, Mersmann S, Buschmann H, Baron JM, Amann PM, Czaja K, Hollert H, Bluhm K, Redelstein R, Bolm C. ChemMedChem 2013; 8: 217 5c Park SJ, Buschmann H, Bolm C. Bioorg. Med. Chem. Lett. 2011; 21: 4888 6a Zhu Y, Loso MR, Watson GB, Sparks TC, Rogers RB, Huang JX, Gerwick BC, Babcock JM, Kelley D, Hegde VB, Nugent BM, Renga JM, Denholm I, Gorman K, DeBoer GJ, Hasler J, Meade T, Thomas JD. J. Agric. Food Chem. 2011; 59: 2950 6b Babcock JM, Gerwick CB, Huang JX, Loso MR, Nakamura G, Nolting SP, Rogers RB, Sparks TC, Thomas J, Watson GB, Zhu Y. Pest. Manag. Sci. 2011; 67: 328 6c Watson GB, Loso MR, Babcock JM, Hasler JM, Letherer TJ, Young CD, Zhu Y, Casida JE, Sparks TC. Insect. Biochem. Mol. Biol. 2011; 41: 432 6d Sparks TC, Loso MR, Watson GB, Babcock JM, Kramer VJ, Zhu Y, Nugent BM, Thomas JD In Modern Crop Protection Compounds . 2nd ed., Vol. 3; Kraemer W, Schirmer U, Jeschke P, Witschel M. Wiley-VCH; Weinheim: 2012: 1226 7 Liberation, Absorption, Distribution, Metabolism, Excretion. 8 Goldberg FW, Kettle JG, Xiong J, Lin D. Tetrahedron 2014; 70: 6613 9 Bolm C, Hackenberger CP. R, Simić O, Verrucci M, Müller D, Bienewald F. Synthesis 2002; 879 10a Johnson CR, Lavergne OM. J. Org. Chem. 1993; 58: 1922 10b Raguse B, Ridley DD. Aust. J. Chem. 1986; 39: 1655 10c Williams TR, Cram DJ. J. Org. Chem. 1973; 38: 20 11 Hendriks CM. M, Bohmann RA, Bohlem M, Bolm C. Adv. Synth. Catal. 2014; 356: 1847 12a Williams TR, Booms RE, Cram DJ. J. Am. Chem. Soc. 1971; 93: 7338 12b Schmidbaur H, Kammel G. Chem. Ber. 1971; 104: 3234 12c Johnson CR, Schroeck CW, Shanklin JR. J. Am. Chem. Soc. 1973; 95: 7424 12d Johnson CR, Corkins HG. J. Org. Chem. 1978; 43: 4136 13a Johnson CR, Rigau JJ, Haake M, McCants Jr D, Keiser JE, Gertsema A. Tetrahedron Lett. 1968; 9: 3719 13b Johnson CR, Haake M, Schroeck CW. J. Am. Chem. Soc. 1970; 92: 6594 14 Greenwald RB, Evans DH. Synthesis 1977; 650 15 Brussaard Y, Olbrich F, Schaumann E. Inorg. Chem. 2013; 52: 13160 For other applications of 9, see: 16a Tamura Y, Ikeda H, Morita I, Tsubouchi H, Ikeda M. Chem. Pharm. Bull. 1982; 30: 1221 16b Franek W, Claus PK. Monatsh. Chem. 1990; 121: 539 Compound 9 is the N-methyl analogue of O-(mesitylenesulfonyl)hydroxylamine (MSH), which is a well-utilized compound in sulfur imidations. However, large-scale applications have raised safety concern. For relevant references, see: 17a Tamura Y, Minamikawa J, Sumoto K, Fujii S, Ikeda M. J. Org. Chem. 1973; 38: 1239 17b Mendiola J, Rincón JA, Mateos C, Soriano JF, de Frutos Ó, Niemeier JK, Davis EM. Org. Process Res. Dev. 2009; 13: 263 18 Bortolini O, Yang SS, Cooks RG. Org. Mass Spectrom. 1993; 28: 1313 19a Alternatively, the formation of the N-alkylsulfiliminium bromides 14 could be explained by reactions of the alkylamines with S-bromosulfonium salts being formed by initial bromine-to-sulfide additions. Here, however, this reaction path appears unlikely as all attempts to promote such process were unsuccessful leading to only complex product mixtures as revealed by NMR spectroscopy. 19b For an early work, see: Tsujihara K, Furukawa N, Oae K, Oae S. Bull. Chem. Soc. Jpn. 1969; 42: 2631 20 Initially, an equimolar mixture of MeNH2, Br2, und t-BuOK (1.4 equiv each) was applied for the imidation of sulfide 8a. Under these conditions, the conversion of 8a was only moderate (59%), and besides sulfiliminium salt 14a small amounts (2%) of sulfoxide 15a were detected. 21 For the thermal stability of sulfiliminium salts, see: Tamura Y, Matsushima H, Minamikawa J, Ikeda M, Sumoto K. Tetrahedron 1975; 31: 3035 22 Oae S, Masuda T, Tsujihara K, Furukawa N. Bull. Chem. Soc. Jpn. 1972; 45: 3586 Supplementary Material Supplementary Material Supporting Information (PDF)
