Biocatalytic Conversion of Cyclic Ketones Bearing α‐Quaternary Stereocenters into Lactones in an Enantioselective Radical Approach to Medium‐Sized Carbocycles. (5th March 2018)

• Record Type: Journal Article
• Authors: Morrill, Charlotte; Jensen, Chantel; Just‐Baringo, Xavier; Grogan, Gideon; Turner, Nicholas J.; Procter, David J.
• Is Part Of: Angewandte Chemie. Volume 130:Number 14(2018)
• Page Start: 3754
• Page End: 3758
• Publication Date: 2018-03-05
• Subjects: Biokatalyse -- Cyclisierungen -- Lactone -- Radikale -- Samarium; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201800121
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Cyclic ketones bearing α‐quaternary stereocenters underwent efficient kinetic resolution using cyclohexanone monooxygenase (CHMO) from Acinetobacter calcoaceticus . Lactones possessing tetrasubstituted stereocenters were obtained with high enantioselectivity (up to >99 % ee ) and complete chemoselectivity. Preparative‐scale biotransformations were exploited in conjunction with a SmI2 ‐mediated cyclization process to access complex, enantiomerically enriched cycloheptan‐ and cycloctan‐1, 4‐diols. In a parallel approach to structurally distinct products, enantiomerically enriched ketones from the resolution with an α‐quaternary stereocenter were used in a SmI2 ‐mediated cyclization process to give cyclobutanol products (up to >99 % ee ).