β-Cyclodextrin-Mediated Acetic Acid Catalyzed Diastereoselective Mannich Reaction in Water

Abstract

A highly efficient diastereoselective Mannich reaction has been carried out in water using a catalytic amount of β-cyclodextrin as a chiral host in the presence of acetic acid to give the corresponding β-aminoketones (Mannich bases) with good yield (up to 98%) and excellent diastereomeric excess (up to >99%). This ­Brønsted acid–chiral cyclodextrin composite catalyzed reaction proceeds in a syn-selective manner with 98:2 syn/anti selectivity when propiophenone is used as the ketone moiety and in an anti-­selective manner with 100:0 (anti/syn) selectivity when cyclohexanone is used.

Key words

mannich bases - diastereoselectivity - cyclodextrins - aqueous medium - supramolecular chemistry

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• 28a General Procedure for the Mannich Reaction of Aldehydes, Amines and Propiophenone: Amine (1 mmol) was added to β-CD (0.1 mmol) dissolved in H₂O (2 mL) and stirred until the inclusion complex was formed and then aldehyde (1 mmol), AcOH (2 mL) and propiophenone (1 mmol) were added successively and stirred at 10 °C for 48 h. A sat. aq NaHCO₃ solution was added to the above reaction mixture, extracted with EtOAc, dried over Na₂SO₄ and concentrated. The product was purified either by recrystal-lization from EtOH–acetone mixture (3:2) or by silica gel column chromatography
• 28b Analytical data of a few typical compounds are given below: (i)3-[(4-Chlorophenyl)amino]-2-methyl-1,3-diphenylpropan-1-one (4a) (Table 2, entry 1): ¹H NMR [300 MHz, CDCl₃, Me₄Si; syn/anti = 98:2 (HPLC)]: δ = 1.20 (d, J = 7.0 Hz, 3 H), 3.92–4.00 (m, 1 H), 4.51 (br s, 1 H), 4.69 (br s, 1 H), 6.37 (d, J = 9.0 Hz, 2 H), 6.96 (d, J = 9.0 Hz, 2 H), 7.24–7.60 (m, 8 H), 7.94 (d, J = 7.5 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃; syn/anti = 98:2): δ = 11.2, 46.7, 59.2, 114.8, 122.2, 126.7, 127.4, 128.2, 128.7, 128.8, 131.6, 133.4, 136.0, 140.9, 145.7, 202.6. HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₂H₂₀ClNO: 372.12; found: 372.42. HPLC: diastereomeric ratio was determined by HPLC with a Chiralcel OD-H column (n-hexane–isopropanol, 90:10; flow rate: 0.3 mL/min; λ = 254 nm); dr (syn/anti) = 98:2. (ii) 2-Methyl-1,3-diphenyl-3-(phenylamino)propan-1-one (Table 2, entry 2): ¹H NMR (300 MHz, CDCl₃, Me₄Si; syn/anti = 91:9): δ = 1.22 (d, J = 6.9 Hz, 3 H), 3.85–4.15 (m, 1 H), 4.46 (br s, 1 H), 4.75 (br s, 1 H), 6.45 (d, J = 8.4 Hz, 2 H), 6.59–6.63 (m, 1 H), 7.00–7.57 (m, 10 H), 7.95 (d, J = 7.5 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃; syn/anti = 91:9): δ = 11.4, 46.9, 59.2, 113.7, 117.5, 126.8, 127.2, 128.2, 128.6, 128.7, 128.9, 133.2, 136.3, 141.9, 147.2, 202.7. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₂H₂₂NO: 316.16; found: 316.50. HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₂H₂₁NO: 338.16; found: 338.42. HRMS: m/z [M + K]⁺ calcd for C₂₂H₂₁NOK: 354.16; found: 354.33. HPLC: diastereomeric ratio was determined by HPLC with a chiralcel OD-H column (n-hexane–isopropanol, 90:10; flow rate: 0.3 mL/min; λ = 254 nm); dr (syn/anti) = 91:9
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