Manganese-Catalyzed Enantioselective Hydrogenation of Simple Ketones Using an Imidazole-Based Chiral PNN Tridentate Ligand

Abstract

A series of Mn(I) catalysts containing imidazole-based chiral PNN tridentate ligands with controllable ‘side arm’ groups have been established, enabling the inexpensive base-promoted asymmetric hydrogenation of simple ketones with outstanding activities (up to 8200 TON) and good enantioselectivities (up to 88.5% ee). This protocol features wide substrate scope and functional group tolerance, thereby providing easy access to a key intermediate of crizotinib.

Key words

manganese - asymmetric hydrogenation - simple ketones - imidazole - tridentate ligand

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• 15 General Procedure for the Preparation of Ligands: A solution of (S _C , R _FC )-1 (1 mmol), benzimidazole aldehyde (1.1 mmol) in anhydrous MeOH was stirred at 60 °C for 10–12 h, The reaction was cooled to room temperature, then NaBH₄ (3 mmol) was added and the mixture was heated to 60 °C again, and stirred at this temperature for 4 h. The solvent was removed under vacuum, and the crude ligand was purified by column chromatography on silica gel. L2: Orange solid (432.0 mg, 75% yield); mp 84–85 °C; [α]_D ²⁰ = +120.0 (c = 0.5, CHCl₃). ¹H NMR (600 MHz, CDCl₃): δ = 7.71 (d, J = 7.8 Hz, 1 H), 7.55–7.53 (m, 2 H), 7.2–7.36 (m, 3 H), 7.21–7.14 (m, 8 H), 7.09–7.07 (m, 3 H), 7.02–6.99 (m, 1 H), 6.85–6.83 (m, 2 H), 5.03 (d, J = 16.8 Hz, 1 H), 4.87 (d, J = 16.8 Hz, 1 H), 4.48 (s, 1 H), 4.31 (s, 1 H), 4.17–4.15 (m, 1 H), 3.95 (s, 5 H), 3.86 (s, 1 H), 3.74 (d, J = 13.8 Hz, 1 H), 3.65 (d, J = 13.8 Hz, 1 H), 1.52 (d, J = 6.6 Hz, 3 H). ¹³C NMR (150 MHz, CDCl₃): δ = 153.1, 142.4, 140.5 (d, J = 10.5 Hz), 137.6 (d, J = 9.0 Hz), 136.6, 135.7, 135.3, 135.1, 132.5, 132.4, 129.2, 128.7, 128.2, 128.12, 128.07, 127.8, 127.5, 126.3, 122.4, 121.8, 119.5, 109.6, 97.8 (d, J = 25.5 Hz), 75.0 (d, J = 9.0 Hz), 71.3 (d, J = 4.5 Hz), 69.7, 69.3, 69.0 (d, J = 4.5 Hz), 51.4 (d, J = 9.0 Hz), 46.4, 44.0, 20.0. ³¹P NMR (162 MHz, CDCl₃): δ = –24.25. HRMS (ESI): m/z [M + H]⁺ calcd for C₃₉H₃₆FeN₃P: 634.2069; found: 634.1996.
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• 18 General Procedure for the Asymmetric Hydrogenation of Ketones Under an argon atmosphere, a vial was charged with Mn(CO)₅Br/L2 (0.1 mol%) and KOH (2 mol%), which were dissolved in dried MeOH (2 mL). The resulting red solution was stirred briefly before the ketone (1 mmol) was added. The vial was placed in an alloy plate that was then placed into an autoclave. The autoclave was purged five times with hydrogen, then pressurized to 3.0 Mpa, and stirred at room temperature for 10 h. After slowly releasing the hydrogen pressure, the solvent was removed, and the mixture was purified by passing through a short column of silica gel to afford the corresponding alcohol. The ee values of all compounds were determined by HPLC analysis with a chiral column. (R)-1-(4-Methoxyphenyl)ethan-1-ol (4k): Colorless oil (150.4 mg, 99% yield); 84.9% ee (R); [α]_D ²⁰ = +41.5 (c = 0.5, CHCl₃). HPLC conditions: Chiralpak OJ-H column, hexane/isopropanol = 95:5; flow rate = 0.8 mL/min; UV detection at 220 nm; (S) = 33.74 min (minor), (R) = 35.98 min (major). ¹H NMR (600 MHz, CDCl₃): δ = 7.25 (d, J = 8.4 Hz, 2 H), 6.84 (d, J = 9.0 Hz, 2 H), 4.78 (q, J = 6.0 Hz, 1 H), 3.76 (s, 3 H), 2.57 (brs, 1 H), 1.43 (d, J = 6.6 Hz, 3 H). ¹³C NMR (150 MHz, CDCl₃): δ = 158.9, 138.1, 126.7, 113.8, 69.8, 55.3, 25.0. (R)-1-(2,6-Dichloro-3-fluorophenyl)ethan-1-ol (4m): Colorless oil (182.2 mg, 88% yield); 85.1% ee (R); [α]_D ²⁰ = –13.1 (c = 0.5, CHCl₃). HPLC conditions: Chiralpak OD-H column, hexane/isopropanol = 90:10 flow rate = 0.8 mL/min; UV detection at 220 nm; (S) = 13.31 min (minor), (R) = 14.02 min (major). ¹H NMR (400 MHz, CDCl₃): δ = 7.32–7.28 (dd, J = 8.8, 4.8 Hz,1 H), 7.06 (dd, J = 16.8, 8.4 Hz, 1 H), 5.64 (q, J = 7.2 Hz, 1 H), 2.84 (brs, 1 H), 1.69 (d, J = 6.8 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 157.3; (¹ J _C–F = 248 Hz), 140.5, 129.6; (³ J _C–F = 7 Hz), 128.3, 121.5, 115.6; (² J _C–F = 23 Hz), 68.4, 21.0.