One‐pot Unsymmetrical Ketone Synthesis Employing a Pyrrole‐Bearing Formal Carbonyl Dication Linchpin Reagent1. (3rd July 2015)

• Record Type: Journal Article
• Authors: Heller, Stephen T.; Newton, James N.; Fu, Tingting; Sarpong, Richmond
• Is Part Of: Angewandte Chemie. Volume 127:Number 34(2015)
• Page Start: 9977
• Page End: 9981
• Publication Date: 2015-07-03
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201502894
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>A one‐pot procedure for the synthesis of unsymmetrical ketones utilizing a pyrrole‐bearing carbonyl linchpin reagent (carbonyl linchpin <italic>N</italic>, <italic>O</italic>‐dimethylhydroxylamine pyrrole; CLAmP) is reported. In contrast to other carbonyl dielectrophile equivalents, CLAmP enables the synthesis of ketones from a variety of organolithium and Grignard reagents. The electrophilic nature of CLAmP enables the addition of less reactive as well as thermally unstable nucleophiles. CLAmP was designed to form kinetically stable tetrahedral intermediates upon the addition of organometallic nucleophiles. Evidence for the existence of persistent tetrahedral intermediates was obtained through in situ IR studies.</p> </abstract>