Aerobic Palladium‐Catalyzed Dioxygenation of Alkenes Enabled by Catalytic Nitrite. (6th November 2014)

• Record Type: Journal Article
• Authors: Wickens, Zachary K.; Guzmán, Pablo E.; Grubbs, Robert H.
• Is Part Of: Angewandte Chemie. Volume 127:Number 1(2015)
• Page Start: 238
• Page End: 242
• Publication Date: 2014-11-06
• Subjects: Alkene -- Hochvalente Palladium‐Komplexe -- Nitrit -- Oxidation -- Sauerstoff; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201408650
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Catalytic nitrite was found to enable carbon–oxygen bond‐forming reductive elimination from unstable alkyl palladium intermediates, providing dioxygenated products from alkenes. A variety of functional groups were tolerated, and high yields (up to 94 %) were observed with many substrates, also for a multigram‐scale reaction. Nitrogen dioxide, which could form from nitrite under the reaction conditions, was demonstrated to be a potential intermediate in the catalytic cycle. Furthermore, the reductive elimination event was probed with 18 O‐labeling experiments, which demonstrated that both oxygen atoms in the difunctionalized products were derived from one molecule of acetic acid. Abstract : Katalytische Mengen an Nitrit ermöglichen die Bildung von C‐O‐Bindungen durch reduktive Eliminierung von instabilen Alkyl‐Palladium‐Intermediaten. Dioxygenierte Produkte lassen sich ausgehend von Alkenen in hohen Ausbeuten erhalten, wobei molekularer Sauerstoff als terminales Oxidationsmittel Verwendung findet. Einblicke in die C‐O‐bindungsbildende reduktive Eliminierung wurden durch 18 O‐Markierung erhalten.