Synlett 2016; 27(13): 1973-1978
DOI: 10.1055/s-0035-1561630
letter
© Georg Thieme Verlag Stuttgart · New York

Nickel(II)-Catalyzed Asymmetric Michael Addition of Oxindoles with Modified N,N,O-Tridentate Chiral Phenanthroline Ligands

Yuki Naganawa*, Hiroki Abe, Hisao Nishiyama*
Further Information

Publication History

Received: 03 March 2016

Accepted after revision: 04 April 2016

Publication Date:
10 May 2016 (eFirst)

Abstract

Nickel(II)-catalyzed enantioselective Michael addition of N-Boc-oxindole derivatives with methyl vinyl ketone was demonstrated to give the corresponding adducts having chiral all-carbon quaternary centers with up to 87% ee in the presence of axially chiral N,N,O-tridentate phenanthroline ligand.

Supporting Information

 
  • References and Notes


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  • 11 Procedure for the Synthesis of Ligand (S)-1c A solution of phen (0.90 g, 5 mmol) in THF (20 mL) was cooled to –78 °C, and PhLi (1.5 equiv, 7.5 mmol) was added dropwise. The resulting black suspension was warmed up to room temperature. After stirring overnight, the reaction mixture was poured into water, and the aqueous phase was extracted with EtOAc. The organic phase was dried over anhydrous MgSO4 and concentrated under reduced pressure. To a stirred solution of the crude product in EtOAc, MnO2 was added at room temperature. The black suspension was kept stirred at 60 °C. After stirring for 6 h, the reaction mixture was filtered by Celite and concentrated under reduced pressure. Purification by column chromatography on silica gel afforded 2-Ph-phen in 58% yield. A solution of (S)-5 (780 mg, 2 mmol) in THF (10 mL) was cooled to –78 °C, and n-BuLi (1.1 equiv, 2.2 mmol) was added dropwise. After stirring for 1 h, 2-Ph-phen (1.1 equiv, 2.2 mmol) was added dropwise. After stirring overnight, the reaction mixture was poured into water, and the aqueous phase was extracted with EtOAc. The organic phase was dried over anhydrous MgSO4 and concentrated under reduced pressure. To a stirred solution of the crude product in EtOAc, MnO2 was added at room temperature. The black suspension was kept stirred at 60 °C. After stirring for 6 h, the reaction mixture was filtrated by Celite and concentrated under reduced pressure. The residue was added MeOH and concd HCl, and heated to 60 °C. After stirring 12 h, the reaction mixture was poured into aq NaHCO3 and the aqueous phase was extracted with EtOAc. Purification by column chromatography on silica gel afforded (S)-1c as a yellow powder in 40% yield. Compound (S)-1c: IR (KBr): 3861, 3450, 3053, 1621, 1591, 1549, 1497, 1469, 1438, 1360, 1306, 1204, 1151, 1106 cm–1. 1H NMR (300 MHz, CDCl3): δ = 8.28 (m, 3 H), 8.14 (d, J = 4.4 Hz, 1 H), 8.05–7.94 (m, 5 H), 7.82–7.79 (m, 1 H), 7.65 (d, J = 4.1 Hz, 1 H), 7.56–7.44 (m, 4 H), 7.37–7.18 (m, 9 H), 7.12–7.07 (m, 2 H), 7.03–7.00 (m, 1 H) (phenolic OH was not observed) ppm. 13C NMR (75 MHz, CDCl3): δ = 156.8, 156.6, 156.1, 143.9, 143.4, 142.4, 140.7, 138.3, 137.4, 136.6, 136.1, 133.6, 133.3, 132.8, 129.9, 129.4, 129.1, 128.9, 128.6, 128.1, 127.9, 127.8, 127.7, 127.6, 127.4, 127.4, 126.85, 126.82, 126.5, 126.3, 126.0, 125.7, 125.2, 122.9, 121.5, 121.1, 119.6, 119.2 ppm. HRMS–FAB: m/z calcd for C24H29N2O [M + H]+: 601.2280; found: 601.2284. [α]D 21 –131.9 (c 0.50, CHCl3).
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  • 13 Crystallographic data obtained for (S)-1c had been deposited with the Cambridge Crystallographic Data Centre. CCDC 1455175 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
  • 14 We also tested this N-methyloxycarbonyl-3-phenyloxindole in the enantioselective hydroxylation reaction with Davis’ oxaziridine in the presence of Cu(II) complex of (S)-1b (ref. 10d). We obtained the corresponding hydroxylated product in 89% yield and with 86% ee. This was the slight lower ee than that of the product in the reaction of N-Boc-3-phenyloxidole 2a (85% yield, 95% ee).
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  • 16 We observed chiral Ni(II) complex of (S)-1c and Ni(OAc)2 in molecular ratio of 1:1 by ESI-MS analysis. At the same time, we did not confirm the other complex of (S)-1c and Ni(OAc)2 in molecular ratio of 2:1. For details, see Supporting Information.
  • 17 General Experimental Procedures for Enantioselective Michael Addition To a mixture of (S)-1c (7.2 mg, 12.0 μmol) and Ni(II) salts (10.0 μmol) in a Schlenk tube under Ar atmosphere, dry CH2Cl2 (0.5 mL) was added at room temperature. After stirring for 30 min at 40 °C, the reaction mixture was cooled to 25 °C, and then oxindole 2 (0.1 mmol) was added at one portion to the mixture. After stirring another 30 min, MVK (25 μL, 0.30 mmol) was subjected at one portion to the mixture and stirred at the 25 °C, the catalyst was removed by passing through short column chromatography on silica gel (eluting CHCl3), and the solvent was evaporated. The residue was purified by column chromatography (eluting hexane–EtOAc or toluene–EtOAc) to give the desired products (R)-4. Compound 4e: IR (KBr): 3414, 1982, 1764, 1732, 1619, 1480, 1465, 1412, 1395, 1371, 1325, 1253, 1148, 1072, 1017 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.97 (d, J = 10.2 Hz, 1 H), 7.58–7.55 (m, 2 H), 7.46–7.38 (m, 2 H), 7.28–7.15 (m, 3 H), 2.80–2.71 (m, 1 H), 2.55–2.31 (m, 2 H), 2.11–2.00 (m, 4 H), 1.64 (s, 9 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 207.0, 176.2, 149.3, 143.5, 140.1, 130.3 (q, J C–F = 32.3 Hz), 129.7, 129.4, 127.7, 125.9 (q, J C–F = 3.7 Hz), 125.3, 124.9, 123.9 (q, J C–F = 228.3 Hz), 115.8, 85.3, 56.1, 38.7, 32.0, 30.3, 28.3 ppm. HRMS–FAB: m/z calcd for C24H24O4NF3 [M + Na]+: 470.1550; found: 470.1534. [α]D 21 +69.0 (c 0.50, CHCl3). The enantiomeric purity of the product was determined by HPLC analysis (Daicel CHIRALPAK AD-H, hexane–i-PrOH = 15:1, flow rate = 1.0 mL min–1): t R (minor) = 6.8 min; t R (major) = 9.8 min; ee 65%. Compound 4j: IR (KBr): 3441, 1979, 1759, 1729, 1511, 1490, 1415, 1511, 1450, 1415, 1369, 1339, 1254, 1153, 1116, 1062, 1011 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.90 (d, J = 8.4 Hz, 1 H), 7.29–7.18 (m, 5 H), 7.04 (d, J = 2.1 Hz, 1 H), 2.86–2.78 (m, 1 H), 2.54–2.12 (m, 9 H), 2.11 (s, 3 H), 1.72 (s, 9 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 207.2, 176.9, 149.4, 137.6, 137.5. 136.8, 134.6, 130.8, 129.6, 129.3, 127.0, 125.2, 115.3, 84.7, 56.1, 39.3, 32.0, 30.6, 28.6, 21.7, 21.5 ppm. HRMS–FAB: m/z calcd for C25H29NO4 [M + Na]+: 430.1994; found: 430.1989. [α]D 21 +64.2 (c 0.10, CHCl3). The enantiomeric purity of the product was determined by HPLC analysis (Daicel CHIRALPAK AD-H, hexane–i-PrOH = 90:10, flow rate = 1.0 mL min–1): t R (minor) = 8.0 min; t R (major) = 13.8 min; ee 80%. Compound 4k: IR (KBr): 3413, 2980, 2839, 1766, 1731, 1608, 1580, 1513, 1483, 1394, 1347, 1254, 1146, 1033 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.94 (dd, J = 8.7, 4.5 Hz, 1 H), 7.21–7.18 (m, 2 H), 7.11–7.04 (m, 1 H), 6.91–6.83 (m, 3 H), 3.78 (s, 3 H), 2.79–2.65 (m, 1 H), 2.43–2.32 (m, 2 H), 2.15–2.08 (m, 1 H), 2.05 (s, 3 H), 1.62 (s, 9 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 207.1, 176.6, 161.9, 159.4, 158.6, 149.5, 135.9 (d, J C-F = 2.3 Hz), 132.8 (d, J C–F = 7.4 Hz), 131.0, 128.2, 117.0 (d, J C–F = 7.4 Hz), 115.6 (d, J C–F = 23.0 Hz), 114.4, 112.2 (d, J C–F = 24.1 Hz), 85.1, 55.6 (d, J C–F = 9.8 Hz), 38.8, 31.8, 30.3, 28.3 ppm. HRMS–FAB: m/z calcd for C24H26FNO5 [M + Na]+: 450.1693; found: 450.1681. [α]D 21 +42.6 (c 0.20, CHCl3). The enantiomeric purity of the product was determined by HPLC analysis (Daicel CHIRALPAK AD-H, hexane–i-PrOH = 90:10, flow rate = 1.0 mL min–1): t R (minor) = 11.3 min; t R (major) = 15.9 min; ee 81%.
  • 18 For a review on Ni(II)-catalyzed enantioselective conjugate addition, see: Pellissier H. Adv. Synth. Catal. 2015; 357: 2745

    • Ni(II)-catalyzed enantioselective conjugate additions of oxindole to nitroolefin have been reported, see:
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