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
,
Ryo Igarashi
,
Hirotsugu Suzuki
,
Shū Kobayashi*
Further Information

Publication History

Received: 10 January 2017

Accepted after revision: 07 February 2017

Publication Date:
08 March 2017 (eFirst)

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


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  • 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.