Efficient Enrichment of Chiral β-Sulfonyl Ketones through Asymmetric β-Elimination

Abstract

Chiral sulfones are important functionalities of various interesting organic compounds. Herein we reported a catalytic enantioselective β-elimination reaction for the first time and realized the kinetic resolution of racemic β-sulfonyl ketones. The resulted enones could be recovered to re-perform the catalytic resolution. This protocol overcame the yield limitation of 50% of resolution procedures. The resulting chiral β-sulfonyl ketones were successfully transformed into corresponding amide, hydrazine, and alcohols with good stereocontrol, demonstrating the application prospect of this reaction system.

Key words

enantioselective β-elimination - chiral sulfone - kinetic resolution

• References

• 1a Doswald S, Estermann H, Kupfer E, Stadler H, Walther W, Weisbrod T, Wirz B, Wostl W. Bioorg. Med. Chem. 1994; 2: 403
• 1b Skarżewski J, Siedlecka R, Wojaczyńska E, Zielińska-Blajet M. Tetrahedron: Asymmetry 2002; 13: 2105
• 1c Teall M, Oakley P, Harrison T, Shaw D, Kay E, Elliott J, Gerhard U, Castro JL, Shearman M, Ball RG, Tsou NN. Bioorg. Med. Chem. Lett. 2005; 15: 2685
• 1d Reck F, Zhou F, Girardot M, Kern G, Eyermann CJ, Hales NJ, Ramsay RR, Gravestock MB. J. Med. Chem. 2005; 48: 499
• 1e Scott JP, Oliver SF, Brands KM. J, Brewer SE, Davies AJ, Gibb AD, Hands D, Keen SP, Sheen FJ, Reamer RA, Wilson RD, Dolling U.-H. J. Org. Chem. 2006; 71: 3086
• 1f Scott JP, Lieberman DR, Beureux OM, Brands KM. J, Davies AJ, Gibson AW, Hammond DC, McWilliams CJ, Stewart GW, Wilson RD, Dolling U.-H. J. Org. Chem. 2007; 72: 4149
• 1g Neamati N, Kabalka GW, Venkataiah B, Dayam R. WO 081966, 2007
• 1h Nielsen M, Jacobsen CB, Holub N, Paixão MW, Jørgensen KA. Angew. Chem. Int. Ed. 2010; 49: 2668
• 2a Bertus P, Phansavath P, Ratovelomanana-Vidal V, Genêt J.-P, Touati AR, Homri T, Ben Hassine B. Tetrahedron Lett. 1999; 40: 3175
• 2b Mauleón P, Carretero JC. Chem. Commun. 2005; 4961
• 2c Zhang H.-L, Hou X.-L, Dai L.-X, Luo Z.-B. Tetrahedron: Asymmetry 2007; 18: 224
• 2d Llamas T, Arrayás RG, Carretero JC. Angew. Chem. Int. Ed. 2007; 46: 3329
• 2e Ding Z, Yang J, Wang T, Shen Z, Zhang Y. Chem. Commun. 2009; 571
• 2f Zhou T, Peters B, Maldonado MF, Govender T, Andersson PG. J. Am. Chem. Soc. 2012; 134: 13592
• 2g Peters BK, Zhou T, Rujirawanich J, Cadu A, Singh T, Rabten W, Kerdphon S, Andersson PG. J. Am. Chem. Soc. 2014; 136: 16557
• 3a Hiroi K, Makino K. Chem. Lett. 1986; 617
• 3b Trost BM, Organ MG, O’Doherty GA. J. Am. Chem. Soc. 1995; 117: 9662
• 3c Gais H.-J, Jagusch T, Spalthoff N, Gerhards F, Frank M, Raabe G. Chem. Eur. J. 2003; 9: 4202
• 3d Ueda M, Hartwig JF. Org. Lett. 2010; 12: 92
• 3e Wu X.-S, Chen Y, Li M.-B, Zhou M.-G, Tian S.-K. J. Am. Chem. Soc. 2012; 134: 14694
• 3f Ma X.-T, Dai R.-H, Zhang J, Gu Y, Tian S.-K. Adv. Synth. Catal. 2014; 356: 2984
• 4a Shimizu I, Ohashi Y, Tsuji J. Tetrahedron Lett. 1984; 25: 5183
• 4b Grigg R. Tetrahedron: Asymmetry 1995; 6: 2475
• 4c Llamas T, Arrayás RG, Carretero JC. Org. Lett. 2006; 8: 1795
• 5a Kennedy M, McKervey MA, Maguire AR, Roos GH. P. J. Chem. Soc., Chem. Commun. 1990; 361
• 5b Honma M, Nakada M. Tetrahedron Lett. 2003; 44: 9007
• 5c Honma M, Sawada T, Fujisawa Y, Utsugi M, Watanabe H, Umino A, Matsumura T, Hagihara T, Takano M, Nakada M. J. Am. Chem. Soc. 2003; 125: 2860
• 5d Takano M, Umino A, Nakada M. Org. Lett. 2004; 6: 4897
• 5e Sawada T, Nakada M. Adv. Synth. Catal. 2005; 347: 1527
• 5f Takeda H, Watanabe H, Nakada M. Tetrahedron 2006; 62: 8054
• 6 Bernabeu MC, Chinchilla R, Falvello LR, Nájera C. Tetrahedron: Asymmetry 2001; 12: 1811
• 7a Mossé S, Alexakis A. Org. Lett. 2005; 7: 4361
• 7b Li H, Song J, Liu X, Deng L. J. Am. Chem. Soc. 2005; 127: 8948
• 7c Liu T.-Y, Long J, Li B.-J, Jiang L, Li R, Wu Y, Ding L.-S, Chen Y.-C. Org. Biomol. Chem. 2006; 4: 2097
• 7d Jin Z, Xu J, Yang S, Song B.-A, Chi YR. Angew. Chem. Int. Ed. 2013; 52: 12354

For selected reviews on kinetic resolution, see:
• 8a Kagan HB, Fiaud JC. Top. Stereochem. 1988; 18: 249
• 8b Keith JM, Larrow JF, Jacobsen EN. Adv. Synth. Catal. 2001; 343: 5
• 8c Vedejs E, Jure M. Angew. Chem. Int. Ed. 2005; 44: 3974
• 9a Patel RN. ACS Catal. 2011; 1: 1056
• 9b Fuchs M, Farnberger JE, Kroutil W. Eur. J. Org. Chem. 2015; 6965
• 9c Kumar R, Martinez C, Martin V, Wong J. Development of Chemoenzymatic Processes: An Industrial Perspective. In Green Biocatalysis . Patel RN. John Wiley and Sons; New York: 2016. 1st ed. 165-178
• 10a Brower KR, Chen JS. J. Am. Chem. Soc. 1965; 87: 3396
• 10b Trost BM. Acc. Chem. Res. 1978; 11: 453
• 10c Stirling CJ. M. Acc. Chem. Res 1979; 12: 198
• 10d Ono N, Tamura R, Nakatsuka T, Hayami J, Kaji A. Bull. Chem. Soc. Jpn. 1980; 53: 3295
• 10e Baskin JM, Wang Z. Tetrahedron Lett. 2002; 43: 8479
• 10f Ye F, Orita A, Doumoto A, Otera J. Tetrahedron 2003; 59: 5635
• 11a Blakemore PR. J. Chem. Soc., Perkin Trans. 1 2002; 2563
• 11b Taylor RJ. K, Casy G. Org. React. (N.Y., Engl. Transl.) 2003; 62: 357
• 11c Carretero JC, Arrayás RG, Adrio J In Organosulfur Chemistry in Asymmetric Synthesis . Wiley-VCH; Weinheim: 2009: 291-320
• 12a Wallace TJ, Hofmann JE, Schriesheim A. J. Am. Chem. Soc. 1963; 85: 2739
• 12b Kocienski PJ, Lythgoe B, Ruston S. J. Chem. Soc., Perkin Trans. 1 1978; 829
• 12c Johnson CR, Kirchhoff RA. J. Am. Chem. Soc. 1979; 101: 3602
• 12d Iwama T, Kataoka T, Muraoka O, Tanabe G. Tetrahedron 1998; 54: 5507
• 12e Gupta L, Ramírez A, Collum DB. J. Org. Chem. 2010; 75: 8392
• 13a Zhong G, Shabat D, List B, Anderson J, Sinha SC, Lerner RA, Barbas CF. III. Angew. Chem. Int. Ed. 1998; 37: 2481
• 13b Gayet A, Bertilsson S, Andersson PG. Org. Lett. 2002; 4: 3777
• 14a Lee JW, Yan H, Jang HB, Kim HK, Park S.-W, Lee S, Chi DY, Song CE. Angew. Chem. Int. Ed. 2009; 48: 7683
• 14b Yan H, Jang HB, Lee J.-W, Kim HK, Lee SW, Yang JW, Song CE. Angew. Chem. Int. Ed. 2010; 49: 8915
• 14c Yan H, Oh J.-S, Song CE. Org. Biomol. Chem. 2011; 9: 8119
• 14d Yan H, Oh JS, Lee J.-W, Song CE. Nat. Commun. 2012; 3 No. 1212; DOI: 10.1038/ncomms2216
• 14e Park SY, Lee J.-W, Song CE. Nat. Commun. 2015; 6, No. 7512; DOI 10.1038/ncomms8512
• 15a Skarżewski J, Zielińska-Błajet M, Turowska-Tyrk I. Tetrahedron: Asymmetry 2001; 12: 1923
• 15b Zielinska-Błajet M, Kowalczyk R, Skarżewski J. Tetrahedron 2005; 61: 5235