Acylboronates in Polarity-Reversed Generation of Acyl Palladium(II) Intermediates

We report a catalytic cross-coupling process between aryl (pseudo)halides and boron-based acyl anion equivalents. This mode of acylboronate reactivity represents polarity reversal, which is supported by the observation of tetracoordinated boronate and acyl palladium(II) species by ¹¹B, ³¹P NMR, and mass spectrometry. A broad scope of aliphatic and aromatic acylboronates has been examined, as well as a variety of aryl (pseudo)halides.

Acylboronates in Polarity-Reversed Generation of Acyl Palladium(II) Intermediates

We report a catalytic cross-coupling process between aryl (pseudo)halides and boron-based acyl anion equivalents. This mode of acylboronate reactivity represents polarity reversal, which is supported by the observation of tetracoordinated boronate and acyl palladium(II) species by ¹¹B, ³¹P NMR, and mass spectrometry. A broad scope of aliphatic and aromatic acylboronates has been examined, as well as a variety of aryl (pseudo)halides.

A new asymmetric activation strategy for hydrazones as acyl anion equivalents in the bimetallic catalyzed carbonyl-ene reaction

A new asymmetric activation strategy for hydrazones as acyl anion equivalents in the dinuclear zinc cooperative catalyzed carbonyl-ene reaction was developed.

Synthesis of (−)-Verbenone-derived Triazolium Salts and Their Application in Enantioselective Intramolecular Stetter Reaction

Two novel chiral verbenone-derived triazolium salts have been synthesized from readily available (−)-verbenone and found to be efficient for the enantioselective intramolecular Stetter reaction. The approach, based on the intramolecular annulation between acyl anion equivalents and Michael acceptors, benefits from broad substrate scope, high chemical and stereochemical efficiency, and operational simplicity. Mono-, and disubstituded chromanone derivatives have been obtained in excellent yields and in a highly stereochemical manner.

Ion-pairing catalysis in the enantioselective addition of hydrazones to N-acyldihydropyrrole derivatives

Quaternary N-acyliminium salts generated from dihydropyrrole derivatives under Brønsted acid catalysis react with hydrazones, the latter participating as masked nucleophilic acyl anion equivalents.

Regio- and stereospecific rhodium-catalyzed allylic alkylation with an acyl anion equivalent: an approach to acyclic α-ternary β,γ-unsaturated aryl ketones

The regio- and stereospecific rhodium-catalyzed allylic alkylation of secondary allylic carbonates with cyanohydrin pronucleophiles facilitates the direct construction of acyclic α-ternary β,γ-unsaturated aryl ketones.