Solvent‐Controlled Rhodium‐Catalyzed C6‐Selective C−H Alkenylation and Alkylation of 2‐Pyridones with Acrylates. Issue 7 (18th April 2019)

• Record Type: Journal Article
• Authors: Hazra, Sunit; Hirano, Koji; Miura, Masahiro
• Is Part Of: Asian journal of organic chemistry. Volume 8:Issue 7(2019)
• Page Start: 1097
• Page End: 1101
• Publication Date: 2019-04-18
• Subjects: C−H activation -- chemodivergence -- pyridones -- rhodium -- synthetic methods; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; 547.005
• DOI: 10.1002/ajoc.201900190
• Languages: English
• ISSNs: 2193-5807

Abstract

Abstract: A solvent‐controlled rhodium‐catalyzed C6‐selective alkenylation and alkylation of 2‐pyridones with acrylates via a pyridine‐directed C−H cleavage was developed. Using DMF as solvent, the C−H alkenylation with acrylates selectively occurs to deliver the corresponding C6‐alkenylated 2‐pyridones in good yields. On the other hand, the C6‐alkylated products are predominantly formed in a more polar and protic solvent, HFIP. Thus, a single set of starting substrates can be divergently transformed to C6‐functionalized 2‐pyridones, which are of potent interest in medicinal and pharmaceutical chemistry. Abstract : At a fork : A Cp*Rh(III)‐catalyzed, pyridine‐directed C6‐selective C−H alkenylation and alkylation of 2‐pyridones has been developed. Using DMF as solvent, the C−H alkenylation with acrylates occurs selectively to deliver the corresponding C6‐alkenylated 2‐pyridones in good yields. On the other hand, the C6‐alkylated products are predominantly formed in a more polar and protic solvent: HFIP. The observed solvent‐dependent product switching can provide divergent access to the C6‐functionalized 2‐pyridones.