Strategic Application and Transformation of ortho-Disubstituted Phenyl and Cyclopropyl Ketones To Expand the Scope of Hydrogen Borrowing Catalysis

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• 作者：James R. Frost ; Choon Boon Cheong ; Wasim M. Akhtar ; Dimitri F. J. Caputo ; Neil G. Stevenson ; Timothy J. Donohoe
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：December 23, 2015
• 年：2015
• 卷：137
• 期：50
• 页码：15664-15667
• 全文大小：449K
• ISSN：1520-5126

文摘

The application of an iridium-catalyzed hydrogen borrowing process to enable the formation of α-branched ketones with higher alcohols is described. In order to facilitate this reaction, ortho-disubstituted phenyl and cyclopropyl ketones were recognized as crucial structural motifs for C–C bond formation. Having optimized the key catalysis step, the ortho-disubstituted phenyl products could be further manipulated by a retro-Friedel–Crafts acylation reaction to produce synthetically useful carboxylic acid derivatives. In contrast, the cyclopropyl ketones underwent homoconjugate addition with several nucleophiles to provide further functionalized branched ketone products.