136932-59-7Relevant academic research and scientific papers
Ketone Synthesis from Benzyldiboronates and Esters: Leveraging α-Boryl Carbanions for Carbon-Carbon Bond Formation
Lee, Boran,Chirik, Paul J.
, p. 2429 - 2437 (2020)
An alkoxide-promoted method for the synthesis of ketones from readily available esters and benzyldiboronates is described. The synthetic method is compatible with a host of sterically differentiated alkyl groups, alkenes, acidic protons α to carbonyl groups, tertiary amides, and aryl rings having common organic functional groups. With esters bearing α-stereocenters, high enantiomeric excess was maintained during ketone formation, establishing minimal competing racemization by deprotonation. Monitoring the reaction between benzyldiboronate and LiOtBu in THF at 23 °C allowed for the identification of products arising from deborylation to form an α-boryl carbanion, deprotonation, and alkoxide addition to form an "-ate" complex. Addition of 4-trifluoromethylbenzoate to this mixture established the α-boryl carbanion as the intermediate responsible for C-C bond formation and ultimately ketone synthesis. Elucidation of the role of this intermediate leveraged additional bond-forming chemistry and enabled the one-pot synthesis of ketones with α-halogen atoms and quaternary centers with four-different carbon substituents.
SYNTHESIS WITH α-HETEROSUBSTITUTED PHOSPHONATE CARBANIONS. XVII. PREPARATION OF DIACYLATED AROMATICS
Zimmer, Hans,Servay, Thomas K.
, p. 201 - 204 (2007/10/02)
Dianions derived from tetraphenyl arylene-bis--bis-phsphonates react with aromatic and heteroaromatic aldehydes to yield bis-acylated aromatics. Key words: α-Heterosubstituted phosphonate carbanions; diacylated heteroaromatics;
