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DOI: 10.1055/s-2007-970774
Design and Synthesis of a Water-Tolerant Chiral Indium Complex: Application to One-Pot Three-Component Mannich-Type Reactions in Water
Publication History
Publication Date:
08 March 2007 (online)
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Abstract
A novel chiral indium(III) camphorsulfonate complex prepared from indium trichloride, allyltributylstannane and (1S)-(+)-10-camphorsulfonic acid has been developed as a water-tolerant Lewis acid to afford high yields (up to 99%) in one-pot three-component Mannich-type reactions in a true water environment.
Key words
chiral indium complex - one-pot three-component Mannich-type reaction - allyltributylstannane
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References and Notes
Crystal Data: C21H39C4InO12S2, M = 804.26, colorless prism. Crystal dimensions: 0.20 × 0.15 × 0.04 mm, monoclinic, space group P2(1), a = 6.9145(2) Å, b = 15.3916(6) Å, c = 15.5826 (6) Å, V = 1657.02(10) Å3, Z = 2, D c = 1.612 Mg/m3. Reflections collected: 34477; independent reflections: 7580 (R int = 0.0432), final R[I > 2σ(I)] = 0.0428, R (all data) = 0.0535, R w = 0.1327. Crystallographic data for this crystal has been deposited with the Cambridge Crystallographic Data Center as supplementary publication number CCDC 624125. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road Cambridge CB2, 1EZ, UK [fax: +44(1223)336033; e-mail: deposit@ccdc.cam.ac.uk].
6Reactions with aliphatic aldehydes or aliphatic amines afforded the products in low yields.
7Typical Reaction Procedure: Anhydrous benzaldehyde (0.05 mL, 0.5 mmol) and indium complex 4 (20 mg, 0.025 mmol) were mixed and stirred at r.t. in H2O (5 mL) for 10 min before the addition of anhyd aniline (0.06 mL, 0.6 mmol). The resulting mixture was stirred at r.t. for 30 min. 1-Methoxy-1-trimethylsilyloxypropene (0.2 mL, 1 mmol) was then added. The suspension was stirred at r.t. for 1 d and then extracted with EtOAc (3 × 25 mL). The organic layers were combined, washed with brine (5 mL), dried over anhyd MgSO4, and concentrated under reduced pressure. The product was obtained in 69% yield after silica gel column chromatography as a yellowish wet solid; R f 0.61 (hexane-EtOAc, 4:1). 1H NMR (CDCl3): δ = 7.23-7.31 (m, 5 H), 7.03-7.10 (m, 2 H), 6.50-6.65 (m, 3 H), 4.53 (s, 1 H), 3.67 (s, 3 H), 1.30 (s, 3 H), 1.20 (s, 3 H). 13C NMR (CDCl3): δ = 176.97, 146.86, 139.17, 128.95, 128.21, 127.93, 127.38, 117.22, 113.34, 64.30, 52.01, 46.95, 24.48, 20.65. FTIR (thin film): 1715.8 cm-1. HRMS: m/z calcd for C18H21NO2: 283.1572; found: 283.1568.
9The drop in reactivity by the fourth or fifth cycle may be attributed to loss of catalyst due to organic extraction.