Enantioselective Silylative Desymmetrization of meso-Indane-1,3-diols Catalyzed by Chiral Guanidines

Abstract

Chiral guanidine-catalyzed desymmetrization of meso-indan-1,3-diols was achieved via enantioselective silylation by using chlorosilanes in good yields with high selectivity. The combination of chlorosilanes and catalysts was determined by the substituents at the C-2 position on the substrate. It was found that the fused phenyl ring on the substrate was essential for achieving high selectivity. The proposed method was found to be applicable to several types of substrates under optimized reaction conditions. Double silylative kinetic resolution with additive Horeau amplification was observed to establish high selectivity.

Key words

desymmetrization - meso-1,3-diols - guanidine - organocatalysis - silylation

Publication History

Received: 23 April 2024

Accepted after revision: 07 May 2024

Accepted Manuscript online:
07 May 2024

Article published online:
27 May 2024

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• 27 Typical Procedure for the Silylative Desymmetrization of meso-2,2-Dimethyl-Indane-1,3-Diol (11, Table [2], Entry 4, as an Example) To a solution of meso-diol 11 (35.6 mg, 0.20 mmol) in THF (1.0 mL) at room temperature was successively added (R)-NMBG (1, 2.5 mg, 10.0 μmol) and i-Pr₂NEt (51.3 μL, 0.30 mmol). After cooling to –78 °C, PhMe₂SiCl (14b, 49.7 μL, 0.30 mmol) was added to the mixture. The reaction mixture was stirred for 24 h, and then the reaction was quenched with saturated aqueous NaHCO₃ at –78 °C and diluted with EtOAc. The organic layer was separated, and the aqueous layer was extracted with EtOAc. The combined organic layers were dried over Na₂SO₄. After filtration of the mixture, the solvent was evaporated and the crude product was purified by preparative thin-layer chromatography on silica (hexane/EtOAc = 4:1) to yield 12b (54.7 mg, 88% yield, 97% ee) as a white solid. The 1 mmol Scale Silylative Desymmetrization of meso-2,2-Dimethyl-Indane-1,3-Diol (11, Table [2], Entry 5) To a solution of meso-diol 11 (178.2 mg, 1.00 mmol) in THF (5.0 mL) at room temperature was successively added (R)-NMBG (1, 12.5 mg, 50.0 μmol) and i-Pr₂NEt (256.4 μL, 1.50 mmol). After cooling to –78 °C, PhMe₂SiCl (14b, 248.7 μL, 1.50 mmol) was added to the mixture. The reaction mixture was stirred for 24 h, and then the reaction was quenched with saturated aqueous NaHCO₃ at –78 °C and diluted with EtOAc. The organic layer was separated, and the aqueous layer was extracted with EtOAc. The combined organic layers were dried over Na₂SO₄. After filtration of the mixture, the solvent was evaporated and the crude product was purified by column chromatography on silica (hexane/EtOAc = 20:1 to 9:1) to yield 12b (250.4 mg, 80% yield, 98% ee) as a white solid