Dual-catalytic structural isomerisation as a route to α-arylated ketones

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Abstract

Abstract Isomerisation reactions provide streamlined routes to organic compounds which are otherwise hard to directly synthesise. The most common forms are positional, geometrical or stereochemical isomerisations which involve the relocation of a double bond or a change in relative location of groups in space. In contrast, far fewer examples of structural (or constitutional) isomerisation exist where the connectivity between atoms is altered. The development of platforms capable of such rearrangement poses a unique set of challenges because chemical bonds must be selectively cleaved, and new ones formed without overall addition or removal of atoms. Here, we show that a dual catalytic system can enable the structural isomerisation of readily available allylic alcohols into more challenging-to-synthesise α-arylated ketones. Key to our strategy is the combination of a cobalt catalyst and photocatalyst under reductive, protic conditions which allows intermediates to propagate catalytic turnover. By providing an unusual disconnection to structural motifs which are difficult to access through direct arylation, we anticipate inspiring other advanced catalytic isomerisation strategies that will further retrosynthetic logic for complex molecule synthesis.

Authors 3

1. Christopher J. Teskey

   Technische Universität Braunschweig

   Affiliation as printed

   Technische Universität Braunschweig

2. Danijela Lunic Aachen Institute of Organic Chemistry

   RWTH Aachen University

   Affiliation as printed

   RWTH Aachen University

   Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany

3. Nikita Vystavkin Aachen Institute of Organic Chemistry

   RWTH Aachen University

   Affiliation as printed

   RWTH Aachen University

   Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany