In 2014, the Donohoe group established that methanol participates in hydrogen borrowing chemistry with a variety of ketones to produce α-branched alkylated products. However, α-alkylation of these substrates using higher alcohols could not be achieved and is relatively rare and underdeveloped. In order to enable higher alcohols to be used for C–C bond formation, ortho-disubstituted phenyl (1) and cyclopropyl (3) ketones were recognised as crucial structural motifs. Following catalytic alkylation, the ortho-disubstituted phenyl products (2) could be manipulated by a retro-Friedel−Crafts acylation reaction to produce multiple carboxylic acid derivatives. Alternatively, the cyclopropyl ketones (4) underwent homoconjugate addition with several nucleophiles to provide further branched ketone products. Other recent advances in this area of chemistry will also be discussed.

Hydrogen borrowing catalysis: Strategic application and transformation of ortho-disubstituted and cyclopropyl ketones

253rd National Meeting (2017)

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