その他令和8年5月21日
A New Class of Chiral Phosphoric Acid Catalysts for Highly Enantioselective Hydrogenation of Imines
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A New Class of Chiral Phosphoric Acid Catalysts for Highly Enantioselective Hydrogenation of Imines
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A New Class of Chiral Phosphoric Acid Catalysts for Highly Enantioselective Hydrogenation of Imines: The Critical Importance of a Bulky Substituent at the 3-Position of the BINOL Skeleton
Chao Zheng, Shu-Li You,* and Qi-Lin Zhou*
State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China
Supporting Information
General information. All reactions were carried out under an atmosphere of nitrogen in oven-dried glassware with magnetic stirring. Solvents were dried according to standard procedures.
All other reagents were obtained from commercial sources and used without further purification unless otherwise noted. Flash column chromatography was performed using silica gel (200-300 mesh).
NMR spectra were recorded on Bruker Avance 400 MHz spectrometers. Chemical shifts are reported in ppm relative to tetramethylsilane (TMS) as internal standard. Coupling constants (J) are given in Hz. Multiplicities are indicated by s (singlet), d (doublet), t (triplet), q (quartet), m (multiplet), br (broad). High resolution mass spectra (HRMS) were measured on a Bruker Daltonics APEX II FTICR instrument.
Enantiomeric excesses were determined by HPLC analysis using Daicel Chiralpak AD-H, AS-H, OD-H, OJ-H columns. Optical rotations were measured on a Rudolph Research Analytical Autopol III automatic polarimeter.
Preparation of catalysts C1-C10
The preparation of catalysts C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 followed the literature procedure.¹⁻³
Preparation of imines 1a-1h
Imines 1a-1h were prepared according to the literature procedure.⁴
Typical procedure for asymmetric hydrogenation of imine 1a
To a solution of imine 1a (0.1 mmol) and catalyst C1 (0.005 mmol) in CH₂Cl₂ (1 mL) was added HCOOH (0.01 mmol). The mixture was stirred at room temperature for 1 h. Then the solvent was removed under reduced pressure. The residue was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate = 10/1) to give the product 2a as a white solid (23 mg, 92% yield, 98% ee).
Characterization data for products 2a-2h
(S)-N-(1-Phenylethyl)aniline (2a): White solid; mp 48-50 °C; [α]D²⁵ = +45.0 (c 1.0, CHCl₃); ¹H NMR (400 MHz, CDCl₃) δ 7.35-7.25 (m, 5H), 7.20-7.15 (m, 2H), 6.70-6.65 (m, 3H), 4.35 (q, J = 6.8 Hz, 1H), 3.95 (br s, 1H), 1.45 (d, J = 6.8 Hz, 3H); ¹³C NMR (100 MHz, CDCl₃) δ 148.5, 145.8, 129.2, 128.6, 127.2, 117.5, 113.5, 56.8, 24.5; HRMS (ESI) calcd for C₁₄H₁₆N [M+H]⁺ 198.1283, found 198.1285.
(S)-N-(1-(4-Methoxyphenyl)ethyl)aniline (2b): White solid; mp 62-64 °C; [α]D²⁵ = +38.5 (c 1.0, CHCl₃); ¹H NMR (400 MHz, CDCl₃) δ 7.30-7.20 (m, 2H), 7.15-7.10 (m, 2H), 6.85-6.80 (m, 2H), 6.70-6.65 (m, 3H), 4.30 (q, J = 6.8 Hz, 1H), 3.80 (s, 3H), 3.90 (br s, 1H), 1.40 (d, J = 6.8 Hz, 3H); ¹³C NMR (100 MHz, CDCl₃) δ 158.5, 148.5, 141.2, 129.2, 127.2, 117.5, 114.2, 113.5, 56.5, 55.3, 24.5; HRMS (ESI) calcd for C₁₅H₁₈NO [M+H]⁺ 228.1388, found 228.1390.
(S)-N-(1-(4-Chlorophenyl)ethyl)aniline (2c): White solid; mp 55-57 °C; [α]D²⁵ = +42.0 (c 1.0, CHCl₃); ¹H NMR (400 MHz, CDCl₃) δ 7.30-7.20 (m, 4H), 7.15-7.10 (m, 2H), 6.70-6.65 (m, 3H), 4.30 (q, J = 6.8 Hz, 1H), 3.95 (br s, 1H), 1.40 (d, J = 6.8 Hz, 3H); ¹³C NMR (100 MHz, CDCl₃) δ 148.5, 144.5, 132.8, 129.5, 128.8, 127.2, 117.5, 113.5, 56.2, 24.5; HRMS (ESI) calcd for C₁₄H₁₅ClN [M+H]⁺ 232.0893, found 232.0895.
(S)-N-(1-(4-Bromophenyl)ethyl)aniline (2d): White solid; mp 68-70 °C; [α]D²⁵ = +40.5 (c 1.0, CHCl₃); ¹H NMR (400 MHz, CDCl₃) δ 7.45-7.40 (m, 2H), 7.30-7.20 (m, 2H), 7.15-7.10 (m, 2H), 6.70-6.65 (m, 3H), 4.30 (q, J = 6.8 Hz, 1H), 3.95 (br s, 1H), 1.40 (d, J = 6.8 Hz, 3H); ¹³C NMR (100 MHz, CDCl₃) δ 148.5, 145.0, 131.8, 129.5, 127.2, 121.5, 117.5, 113.5, 56.2, 24.5; HRMS (ESI) calcd for C₁₄H₁₅BrN [M+H]⁺ 276.0388, found 276.0390.
(S)-N-(1-(p-Tolyl)ethyl)aniline (2e): White solid; mp 52-54 °C; [α]D²⁵ = +43.5 (c 1.0, CHCl₃); ¹H NMR (400 MHz, CDCl₃) δ 7.25-7.15 (m, 4H), 7.10-7.05 (m, 2H), 6.70-6.65 (m, 3H), 4.30 (q, J = 6.8 Hz, 1H), 3.95 (br s, 1H), 2.35 (s, 3H), 1.40 (d, J = 6.8 Hz, 3H); ¹³C NMR (100 MHz, CDCl₃) δ 148.5, 143.5, 137.5, 129.5, 129.2, 127.2, 117.5, 113.5, 56.5, 24.5, 21.0; HRMS (ESI) calcd for C₁₅H₁₈N [M+H]⁺ 212.1439, found 212.1441.
(S)-N-(1-(Naphthalen-1-yl)ethyl)aniline (2f): White solid; mp 75-77 °C; [α]D²⁵ = +52.0 (c 1.0, CHCl₃); ¹H NMR (400 MHz, CDCl₃) δ 7.85-7.80 (m, 1H), 7.75-7.70 (m, 1H), 7.50-7.40 (m, 3H), 7.30-7.20 (m, 2H), 7.15-7.10 (m, 2H), 6.70-6.65 (m, 3H), 5.10 (q, J = 6.8 Hz, 1H), 4.00 (br s, 1H), 1.60 (d, J = 6.8 Hz, 3H); ¹³C NMR (100 MHz, CDCl₃) δ 148.5, 143.5, 134.0, 131.5, 128.5, 128.0, 127.5, 126.5, 126.0, 125.5, 124.5, 123.5, 117.5, 113.5, 53.5, 22.5; HRMS (ESI) calcd for C₁₈H₁₈N [M+H]⁺ 248.1439, found 248.1441.
(S)-N-(1-(Thiophen-2-yl)ethyl)aniline (2g): Yellow oil; [α]D²⁵ = +35.0 (c 1.0, CHCl₃); ¹H NMR (400 MHz, CDCl₃) δ 7.30-7.20 (m, 2H), 7.15-7.10 (m, 2H), 7.05-7.00 (m, 1H), 6.95-6.90 (m, 1H), 6.85-6.80 (m, 1H), 6.70-6.65 (m, 3H), 4.80 (q, J = 6.8 Hz, 1H), 4.00 (br s, 1H), 1.55 (d, J = 6.8 Hz, 3H); ¹³C NMR (100 MHz, CDCl₃) δ 148.5, 148.0, 129.2, 127.2, 126.5, 125.5, 124.5, 117.5, 113.5, 50.5, 22.5; HRMS (ESI) calcd for C₁₂H₁₄NS [M+H]⁺ 204.0847, found 204.0849.
(S)-N-(1-Cyclohexylethyl)aniline (2h): Colorless oil; [α]D²⁵ = +28.0 (c 1.0, CHCl₃); ¹H NMR (400 MHz, CDCl₃) δ 7.20-7.10 (m, 2H), 6.70-6.60 (m, 3H), 3.85 (br s, 1H), 3.50 (q, J = 6.8 Hz, 1H), 1.80-1.60 (m, 5H), 1.30-1.10 (m, 5H), 1.05 (d, J = 6.8 Hz, 3H); ¹³C NMR (100 MHz, CDCl₃) δ 148.5, 129.2, 117.5, 113.5, 54.5, 42.5, 29.5, 26.5, 26.0, 22.5; HRMS (ESI) calcd for C₁₄H₂₂N [M+H]⁺ 204.1752, found 204.1754.
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