Chiral Bis(imidazolidine)iodobenzene (I-Bidine) Organocatalyst for Thiochromane Synthesis Using an Asymmetric Michael/Henry Reaction

Abstract

Bis(imidazolidine)iodobenzene (I-Bidine) was designed as an organocatalyst based on previously reported imidazolidine- or oxazolidine-containing chiral metal catalysts. I-Bidine showed catalytic activity for the Michael/Henry reaction of thiosalicyl aldehydes with nitroalkenes to give optically active thiochromanes with moderate enantiomeric excesses.

Key words

organocatalyst - thiochromane - tandem reaction - asymmetric synthesis

• References and Notes

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• 11 Synthesis of I-Bidines (1); General Procedure: To a stirred solution of 2-iodoisophthalaldehyde (1 equiv) in CH₂Cl₂ (0.067 M) were added monoarylmethyl-(1R,2R)-1,2-diphenylethane-1,2-diamine (2.2 equiv), and AcOH (2.2 equiv) at rt. After being stirred for appropriate time, the reaction mixture was quenched by H₂O, and extracted with CH₂Cl₂. The combined organic layers were washed with brine, dried over Na₂SO₄, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to afford the product. I-Bidine (1a): ¹H NMR (400 MHz, CDCl₃): δ = 7.98 (d, J = 7.2 Hz, 2 H), 7.21–7.43 (m, 21 H), 7.00–7.08 (m, 6 H), 6.94 (d, J = 7.4 Hz, 4 H), 5.31 (s, 2 H), 4.29 (d, J = 7.9 Hz, 2 H), 3.77 (d, J = 8.1 Hz, 2 H), 3.70 (d, J = 13.7 Hz, 2 H), 3.62 (d, J = 13.9 Hz, 2 H), 2.27 (br s, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 143.9, 141.7, 139.8, 135.6, 129.9, 129.3, 128.5, 128.4, 128.2, 128.1, 127.6, 127.5, 127.10, 127.06, 126.7, 106.4, 84.0, 75.4, 68.5, 53.5. HRMS: m/z [M + H]⁺ calcd for C₅₀H₄₆IN₄: 829.2762; found: 829.2771. IR (neat) 3083, 3060, 3027, 2972, 2926, 2844, 1602, 1494, 1454, 1048, 880, 759, 699 cm^–1.
• 12 Crystal Data for I-Bidine (1a): C₅₀H₄₅IN₄: MW = 828.80, monoclinic, P₂₁, a = 10.1466(13) Å, b = 12.5687(15) Å, c = 16.297(2) Å; α = 90°, β = 101.573(2)°, γ = 90°, V = 2036.1(4) ų, Z = 2, R = 0.0390 and wR = 0.0647. CCDC 1425335 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.
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• 14 General Procedure for Asymmetric Michael/Henry Reaction: To a two-necked round-bottomed flask were added I-Bidine (0.015 mmol), nitrostyrene (0.15 mmol), and anhyd toluene (1 mL) under argon, and the mixture was cooled to –40 °C. Slow addition of 2-mercaptobenzaldehyde (0.225 mmol, ca. 75% purity) in anhyd toluene (5 mL) using syringe pump was conducted for 15 h. Then the completion of the reaction was checked by TLC and the solvent was removed under reduced pressure. Yield and diastereomeric ratio of the product were determined by crude ¹H NMR. The crude mixture was purified by silica gel column chromatography to afford the 2-aryl-3-nitrothiochroman-4-ol. The enantiomeric excesses of the product were determined by chiral stationary phase HPLC using a Daicel Chiralpak AD-H, AS-H, and Chiralcel OD-H column. (2R,3S,4R)-3-Nitro-2-phenylthiochroman-4-ol (anti-4a): ¹H NMR (400 MHz, acetone-d ₆): δ = 7.72–7.74 (m, 1 H), 7.53 (dd, J = 1.6, 8.5 Hz, 2 H), 7.36–7.43 (m, 3 H), 7.22–7.29 (m, 2 H), 7.11–7.14 (m, 1 H), 5.69 (d, J = 8.3 Hz, 1 H), 5.36–5.45 (m, 2 H), 5.15 (d, J = 10.8 Hz, 1 H). ¹³C NMR (125 MHz, acetone-d ₆): δ = 136.4, 135.9, 132.5, 130.0, 129.8, 129.3, 129.1, 128.6, 126.0, 125.4, 94.1, 72.3, 47.4. HRMS: m/z [M + NH₄]⁺ calcd for C₁₅H₁₇N₂O₃S: 305.0954; found: 305.0954. IR (neat): 3380, 3062, 3024, 1587, 1555, 1037, 753, 741, 702 cm^–1. [α]_D ²⁶.⁵ +7.0 (c = 0.05, MeOH, 53% ee); enantiomeric excess was determined by HPLC with a Chiralpak AD-H column [hexane–2-propanol (85:15), flow rate: 0.7 mL/min, λ = 254 nm]; t _R (minor enantiomer) = 16.4 min, t _R (major enantiomer) = 17.7 min; 53% ee. (2R,3S,4S)-3-Nitro-2-phenylthiochroman-4-ol (syn-4a): ¹H NMR (400 MHz, acetone-d ₆): δ = 7.59–7.62 (m, 2 H), 7.49 (dd, J = 1.6, 7.6 Hz, 1 H), 7.33–7.43 (m, 3 H), 7.30 (dt, J = 1.5, 7.6 Hz, 1 H), 7.20 (dt, J = 1.4, 7.5 Hz, 1 H), 7.15 (dd, J = 1.4, 7.9 Hz, 1 H), 5.71 (dd, J = 2.9, 11.7 Hz, 1 H), 5.48 (d, J = 5.8 Hz, 1 H), 5.41 (dd, J = 2.9, 5.6 Hz, 1 H), 5.28 (d, J = 11.7 Hz, 1 H). ¹³C NMR (100 MHz, acetone-d ₆): δ = 137.7, 134.5, 133.5, 132.0, 129.9, 129.6, 129.22, 129.19, 125.7, 125.4, 90.1, 70.6, 41.4. HRMS: m/z [M + NH₄]⁺ calcd for C₁₅H₁₇N₂O₃S: 305.0954; found: 305.0957. IR (neat): 3389, 3061, 2925, 2853, 1702, 1644, 1586, 1555, 1520, 1439, 1316, 1036, 762 cm^–1. [α]_D ²⁵.⁹ +78.9 (c = 0.05, MeOH, 69% ee); enantiomeric excess was determined by HPLC with a Chiralpak AD-H column [hexane:2-propanol (85:15), flow rate: 0.7 mL/min, λ = 254 nm]; t _R (minor enantiomer) = 21.4 min; t _R (major enantiomer) = 14.2 min; 69% ee.