Synlett 2017; 28(11): 1287-1290
DOI: 10.1055/s-0036-1588737
cluster
© Georg Thieme Verlag Stuttgart · New York

Catalytic Asymmetric Direct-Type 1,4-Addition Reactions of Alkanesulfonamides

Yasuhiro Yamashita
Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan   Email: shu_kobayashi@chem.s.u-tokyo.ac.jp
,
Ryo Igarashi
Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan   Email: shu_kobayashi@chem.s.u-tokyo.ac.jp
,
Hirotsugu Suzuki
Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan   Email: shu_kobayashi@chem.s.u-tokyo.ac.jp
,
Shū Kobayashi*
Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan   Email: shu_kobayashi@chem.s.u-tokyo.ac.jp
› Author Affiliations
Further Information

Publication History

Received: 10 January 2017

Accepted after revision: 07 February 2017

Publication Date:
08 March 2017 (online)


Abstract

Catalytic asymmetric 1,4-addition reactions of alkanesulfonamides were developed on the ‘product base’ strategy. Alkanesulfonamides reacted with α,β-unsaturated amides in good to high yields with good to high diastereo- and enantioselectivities using a chiral alkaline metal amide. To our knowledge, this is the first example of a catalytic asymmetric C–C bond-forming reaction using an alkanesulfonamide without any activating group at its α-position.

Supporting Information

 
  • References and Notes

    • 1a Comprehensive Organic Synthesis . Trost BM. Pergamon Press; Oxford: 1991
    • 1b Comprehensive Organic Synthesis . Knochel P, Molander GA. Elsevier Science; Oxford: 2014. 2nd ed.
    • 1c Kobayashi S, Matsubara R. Chem. Eur. J. 2009; 15: 10694-10694
    • 2a Trost BM. Science 1991; 254: 1471-1471
    • 2b Trost BM. Angew. Chem. Int. Ed. 1995; 34: 259-259
    • 2c Handbook of Green Chemistry . Anastas PT. Wiley-VCH; Weinheim: 2009

      For a review, see:
    • 3a Kumagai N, Shibasaki M. Angew. Chem. Int. Ed. 2011; 50: 4760-4760

    • For leading examples of this research area, see:
    • 3b Yamada YM. A, Yoshikawa N, Sasai H, Shibasaki M. Angew. Chem. Int. Ed. 1997; 36: 1871-1871
    • 3c Yoshikawa N, Yamada YM. A, Das J, Sasai H, Shibasaki M. J. Am. Chem. Soc. 1999; 121: 4168-4168
    • 3d Trost BM, Ito H. J. Am. Chem. Soc. 2000; 122: 12003-12003
    • 4a Supuran CT, Casini A, Scozzafava A. Med. Res. Rev. 2003; 23: 535-535
    • 4b Milewski S, Hoffmann M, Andruszkiewicz R, Borowski E. Bioorg. Chem. 1997; 25: 283-283
    • 4c Sasikumar TK, Burnett DA, Asberom T, Wu W.-L, Bennett C, Cole D, Xu R, Greenlee WJ, Clader J, Zhang L, Hyde L. Bioorg. Med. Chem. Lett. 2010; 20: 3645-3645
  • 5 pK a value of the α-hydrogen atom of an alkanesulfonamide without any activating group at its α-position is estimated to be >30 in DMSO based on comparison of pK a values of N-methyl-N-phenyl-α-phenylmethanesulfonamide (24.1), tert-butyl phenyl­acetate (23.6), and tert-butyl acetate (30.3). The values are shown in the Bordwell pK a table (http://www.chem. wisc.edu/areas/reich/pkatable/). See also: Bordwell FG. Acc. Chem. Res. 1988; 21: 456-456
    • 6a Chodkiewicz W, Cadiot P, Willemart A. Bull. Soc. Chim. Fr. 1958; 1586-1586
    • 6b Mårtensson O, Nilsson E. Acta Chem. Scand. 1960; 14: 1151-1151
    • 6c Corey EJ, Chaykovsky M. J. Am. Chem. Soc. 1965; 87: 1345-1345
    • 6d Böhme H, Stammberger W. Justus Liebigs Ann. Chem. 1972; 754: 56-56
    • 6e Christensen LW, Seaman JM, Truce WE. J. Org. Chem. 1973; 38: 2243-2243
    • 6f Nkunya MH. H, Zwanenburg B. Recl. Trav. Chim. Pays-Bas 1985; 104: 253-253
    • 6g Mladenova M. Synth. Commun. 1986; 16: 1089-1089
    • 6h Mladenova M, Biserkova M, Kaneti J. Phosphorus, Sulfur Silicon Relat. Elem. 1995; 104: 151-151
    • 6i Velázquez F, Arasappan A, Chen K, Sannigrahi M, Venkatraman S, McPhail AT, Chan T.-M, Shih N.-Y, Njoroge FG. Org. Lett. 2006; 8: 789-789
    • 6j Zeevaart JG, Parkinson CJ, Koning CB. Tetrahedron Lett. 2005; 46: 1597-1597
    • 6k Grimm JB, Katcher MH, Witter DJ, Northrup AB. J. Org. Chem. 2007; 72: 8135-8135
    • 6l Zhou G, Ting P, Aslanian R, Piwinski JJ. Org. Lett. 2008; 10: 2517-2517

    • Review of this research area, see:
    • 6m Postel D, Nhien AN. V, Marco JL. Eur. J. Org. Chem. 2003; 3713-3713
  • 7 Yamashita Y, Kobayashi S. Chem. Eur. J. 2013; 19: 9420-9420
    • 8a Yamashita Y, Suzuki H, Kobayashi S. Org. Biomol. Chem. 2012; 10: 5750-5750
    • 8b Suzuki H, Sato I, Yamashita Y, Kobayashi S. J. Am. Chem. Soc. 2015; 137: 4336-4336
    • 8c Yamashita Y, Sato I, Suzuki H, Kobayashi S. Chem. Asian J. 2015; 10: 2143-2143
    • 8d Sato I, Suzuki H, Yamashita Y, Kobayashi S. Org. Chem. Front. 2016; 3: 1241-1241

      Reviews for catalytic asymmetric addition reactions to α,β-unsaturated amides, see:
    • 9a Byrd KM. Beilstein J. Org. Chem. 2015; 11: 530-530
    • 9b Kumagai N, Shibasaki M. Chem. Eur. J. 2016; 22: 15192-15192
  • 10 Experimental procedure for the reaction of 1c with 2b to afford 1,4-adduct 3cb (Table 2, entry 11) is described as a general method. Under an argon atmosphere, KHMDS (8.0 mg, 0.040 mmol), (R,R)-34-crown-10 (L2, 19.6 mg, 0.0220 mmol), and 1c (81.3 mg, 0.400 mmol) were placed in a well-dried 10 mL one-neck flask with a three-way stopcock, and ethylbenzene (1.0 mL) was added at –78 °C. After stirring for 1 h at the same temperature, 2b (109.8 mg, 0.800 mmol) in ethylbenzene (1.0 mL) was added, and the whole was stirred for 18 h. After addition of water (1 mL) to stop the reaction, the mixture was extracted with CH2Cl2 (30 mL) three times. The organic layers were combined, dried over Na2SO4, and concentrated under reduced pressure after filtration. The crude product obtained was purified by column chromatography (silica gel, hexanes–EtOAc = 1:1) to afford the desired product 3cb (125.4 mg, 92%). Analytical Data of 3cb Colorless solid; mp 91–94 °C. [α]D +27.7 (c 0.102, CHCl3, 82% ee). HPLC analysis using Daicel Chiralpak AS-3 column (Hex–2-PrOH = 9:1, 1.0 mL/min, 210 nm): t R = 20.2 min (minor), 23.5 min (major). 1H NMR (600 MHz, CDCl3): δ = 7.24 (2 H, t, J = 7.6 Hz), 7.20 (2 H, d, J = 6.9 Hz), 7.15 (1 H, t, J = 7.2 Hz), 3.89–3.86 (1 H, m), 3.36 (1 H, dq, J = 14.0, 3.3 Hz), 3.32–3.20 (3 H, m), 3.18–3.13 (2 H, m), 2.83 (6 H, s), 2.83 (3 H, s), 2.75 (1 H, dd, J = 16.0, 10.0 Hz), 1.27 (3 H, d, J = 6.9 Hz), 1.10 (3 H, t, J = 7.2 Hz), 0.91 (3 H, t, J = 6.9 Hz). 13C NMR (100 MHz, CDCl3): δ = 169.6, 141.0, 128.4, 128.0, 126.9, 60.0, 41.8, 40.1, 37.5, 32.0, 14.2, 12.8, 11.0. IR (KBr disc): 3435, 3255, 3060, 2980, 2939, 2814, 2448, 2269, 1994, 1832, 1638, 1459, 1378, 11319, 1270, 1245, 1220, 1199, 1140, 1076, 1041, 965, 927, 878, 804, 767, 741, 711, 687, 622, 601, 559, 527, 504, 452 cm–1. ESI-HRMS: calcd for C17H26N2NaO3S [M + Na]+: 363.1718; found: 363.1733.