Catalytic Asymmetric Intramolecular Bromolactonization of α,β-Unsaturated Ketones

Abstract

Enantioselective bromolactonization by using an amino-urea catalyst to generate the important bromo-containing 3,4-dihydroisocoumarins is described. Excellent yields and good enantioselectivities could be achieved for various 3,4-dihydroisocoumarin compounds.

Key words

3,4-dihydroisocoumarins - bromolactonization - organocatalyst - enantioselectivity - deactivated olefins

• References and Notes


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• 13 The details are presented in the Supporting Information. CCDC 1911858 contains supplementary crystallographic data for compound 4b. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
• 14 General Procedure for Bromolactonization. To a PhMe/CHCl₃ (4 mL/1 ml) solution of α,β-unsaturated ketone (0.1 mmol, 1.0 equiv) and catalyst (7.1 mg, 0.15 mmol, 0.15 equiv) at 15°C, in dark under nitrogen was added halogen source (0.13 mmol, 1.3 equiv). The resulting mixture was stirred at 15°C and monitored by TLC. The reaction was quenched with saturated Na₂SO₃ (1 mL) at 15oC and then was warm to room temperature. The solution was diluted with water (3 mL) and extrated with EtOAc, dried over MgSO₄ and concentrated in vacuo. The residue was purified by flash column chromatography (hexane/EtOAc=3:1) to yield the corresponding lactone. Supporting Information provides full details and graphical guide.