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Unexpected Substituent Effects in Spiro-Compound Formation: Steering N-Aryl Propynamides and DMSO toward Site-Specific Sulfination in Quinolin-2-ones or Spiro[4,5]trienones.

ABSTRACT: A highly substituent-dependent rearrangement allows for the novel and SOCl₂-induced divergent synthesis of 3-methylthioquinolin-2-ones and 3-methylthiospiro[4.5]trienones through intramolecular electrophilic cyclization of N-aryl propyamides. DMSO acts as both solvent and sulfur source, and use of DMSO-h₆/d₆ enables the incorporation of SCH₃ or SCD₃ moieties to the 3-position of the heterocyclic framework. Different para-substituents trigger divergent reaction pathways leading to the formation of quinolin-2-ones for mild substituents and spiro[4,5]trienones for both electron-withdrawing and -donating substituents, respectively. On the basis of both computational and experimental results, a new mechanism has been put forward that accounts for the exclusive spirolization/defluorination process and the surprising substituent effects.

SUBMITTER: Li X

PROVIDER: S-EPMC8291627 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Eco-compatible sonochemical synthesis of 8-aryl-7,8-dihydro-[1,3]-dioxolo[4,5-g]quinolin-6(5H)-ones using green TiO2.

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