Optimization of Manganese Coupling Reaction for Kilogram-Scale Preparation of Two Aryl-1,3-dione Building Blocks

Tomas Smejkal, Vijayagopal Gopalsamuthiram, Sujit K. Ghorai, Anup M. Jawalekar, Dinesh Pagar, Krishna Sawant, Srinivas Subramanian, Jonathan Dallimore, Nigel Willetts, James N. Scutt, Louisa Whalley, Matthew Hotson, Anne Marie Hogan, George Hodges

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

Aryl-1,3-diones represent a promising new class of herbicidal acetyl-CoA carboxylase (ACCase) inhibitors. The original synthesis of this structural motif employed in the research phase involved a selenium oxide mediated oxidation, the use of diazoacetate and aryl lead reagents, and a low temperature oxidation of an aryl lithium intermediate, so it was not well suited to large scale synthesis. For kilogram scale synthesis of the two aryl-1,3-dione building blocks (3 and 4), we developed an alternative route which employs a manganese or manganese-copper catalyzed alkyl Grignard coupling and a semi-pinacol rearrangement of an epoxide as the key steps. The optimized conditions could be of general interest as scalable methods for the synthesis of 2-alkyl substituted benzaldehydes and of 2-aryl-1,3-diones.

Original languageEnglish (US)
Pages (from-to)1625-1632
Number of pages8
JournalOrganic Process Research and Development
Volume21
Issue number10
DOIs
StatePublished - Oct 20 2017

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