A imple oute to 7-ubstituted Quinolin-2()-ones from -ubstituted nilines

Meta -substituted anilines are condensed with methyl 3,3-dimethoxypropionate in a two-step acylation, cyclization sequence to preferentially form 7-substituted quinolinones in an isomeric mixture with 5-substituted quinolinones. The product ratios in this previously unexplored class of substrates depend on the steric and electronic properties of the aniline substituent. Within a series of halogenated anilines, selectivity varies directly with electronegativity and inversely with C–X bond length, up to 93:7 (R = F). For alkyl substituted anilines, a Charton analysis reveals a linear free-energy relationship between steric bulk of the alkyl substituent and selectivity for 7-substituted products, where selectivity for 7-substituted products increases with steric bulk of the alkyl substituent. Alkyl substituted quinolinones are generated with up to 97:3 selectivity for the 7-substituted product when R = t Bu. To create your abstract, type over the instructions in the template box below. Fonts or abstract dimensions should not be changed or altered. • Exclusively 7-substituted quinolinones are made from meta-substituted anilines. • Most anilines produce an isomeric mixture of quinolinones, favoring 7-substitution. • Bulkier aniline substituents yield greater preference for 7-substituted quinolinone.