Photocatalytic Aerobic Phosphatation of Alkenes. Issue 9 (17th January 2018)

• Record Type: Journal Article
• Authors: Depken, Christian; Krätzschmar, Felix; Rieger, Rene; Rode, Katharina; Breder, Alexander
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 9(2018)
• Page Start: 2459
• Page End: 2463
• Publication Date: 2018-01-17
• Subjects: alkenes -- chalcogen Lewis acids -- hydrogen phosphates -- oxidation -- photoredox catalysis; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201711599
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A catalytic regime for the direct phosphatation of simple, non‐polarized alkenes has been devised that is based on using ordinary, non‐activated phosphoric acid diesters as the phosphate source and O2 as the terminal oxidant. The title method enables the direct and highly economic construction of a diverse range of allylic phosphate esters. From a conceptual viewpoint, the aerobic phosphatation is entirely complementary to traditional methods for phosphate ester formation, which predominantly rely on the use of prefunctionalized or preactivated reactants, such as alcohols and phosphoryl halides. The title transformation is enabled by the interplay of a photoredox and a selenium π‐acid catalyst and involves a sequence of single‐electron‐transfer processes. Abstract : Once in a blue moon : The aerobic dehydrogenative coupling of simple hydrogen phosphates with non‐activated alkenes generates a diverse range of allylic phosphates through the catalytic interplay of a photosensitizer (PS) and a chalcogen Lewis acid (Se). In addition to its operational simplicity and high chemoselectivity, the title reaction also enables the facile consecutive redox alkylation of olefins with organocuprates.