Unusual Ambiphilic Carbenoid Equivalent in Amide Cyclopropanation.

Yan, Shiuan; Hsieh, I-Lin; Yan, Tong

doi:10.1002/chin.200640028

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2023

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“…However, using CH 2 Cl 2 or CD 2 Cl 2 resulted in a mixture of the ketone and cyclopropanol products (3ao vs 3ap, 3aq vs 3ar), possibly due to the cyclopropanation of the in situ generated enol ether with the plausible amphiphilic titanium carbene complexes. 26 Next, we also briefly investigated the scope of carboxylic esters and amides in this Ti-catalyzed ketone synthesis (Scheme 2). Amides are among the most important organic compounds widely occurring in medicine, biochemistry, and material science.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Ti-Catalyzed Modular Ketone Synthesis from Carboxylic Derivatives and gem-Dihaloalkanes

Xia

et al. 2023

J. Am. Chem. Soc.

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Ketones are ubiquitous in organic synthesis. However, the general method to convert widely available carboxylic acids, unactivated esters, and amides into ketones remains elusive. Herein, we describe the Ti-catalyzed modular ketone synthesis from carboxylic derivatives and easily accessed gem-dihaloalkanes. Notably, this protocol could achieve the direct catalytic olefination of carboxylic acids. This method features a sequence of olefination and electrophilic transformation and good functional group compatibility and allows rapid access to various functionalized ketones. Preliminary mechanistic studies provide insights into the reaction pathway and support the intermediacy of plausible alkylidene titanocene and gem-bimetallic complexes.

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Section: ■ Results and Discussionmentioning

confidence: 99%