Enones from Acid Fluorides and Vinyl Triflates by Reductive Nickel Catalysis

Abstract

A nickel-catalyzed reductive coupling between acid fluorides and vinyl triflates has been described. This method provides an efficient access to various enones and avoids the requirement for acyl or vinyl metallic reagents in the conventional approaches. The reaction proceeds with a broad range of acid fluorides and cyclic vinyl triflates, tolerating several functional groups. The utility of this synthetic method has been demonstrated by the late-stage modification of pharmaceuticals and biologically active natural compounds.

Metal‐Terpyridine Complexes in Catalytic Application – A Spotlight on the Last Decade

“…In this context, Pan et al . showed the first example for a Ni(0)‐catalyzed electrophile‐electrophile cross‐coupling reaction using acid fluorides and vinyl triflates as reactants (Scheme a) . As in the previous case, the catalytically active species was generated in situ from a Ni(II) precursor and tri‐ t Bu‐tpy was identified as the most versatile ligand (tpy and 4′‐ t Bu‐tpy as well as bidentate polypyridyl ligands gave lower yields).…”

“… (a) Schematic representation of the Ni(0)‐catalyzed cross‐coupling of acid fluorides and vinyl triflates . (b) Schematic representation of selected examples where this reaction has been applied for the late‐stage modification of complex molecules …”

Formation of trisubstituted buta-1,3-dienes and α,β-unsaturated ketones via the reaction of functionalized vinyl phosphates and vinyl phosphordiamidates with organometallic reagents

“…24 Therefore, signicant research efforts have been dedicated to identifying a novel approach to conjugated enones. 25 Nickel-catalyzed 1,2-acyl migration, 26 nucleophilic addition to enones, 27 the crosscoupling reaction between acid uorides and vinyl triates, 28 and carbonyl group olenations 29 are examples of such reactions. The conversion of the vinyl phosphordiamidate 2e into the ketone 4a observed in our study represents a hitherto undescribed reaction of phosphordiamidate en route to becoming a,b-unsaturated ketones.…”

Palladium‐Catalyzed Annulation of Acyl Fluorides with Norbornene via Decarbonylation and CO Reinsertion

“…Transition-metal-catalyzed transformations of carboxylic acid derivatives are attractive methods for the construction of CÀC bonds in organicc hemistry. [1,2] Recently,t he use of acyl fluorides in these transformations has become the subjecto fi ntense research effort, [3][4][5][6][7][8][9][10][11][12] as acyl fluorides are versatile acyl electrophiles with good stability and high reactivity toward nucleophiles. [3,4] One striking aspect of using acyl fluorides in CÀCb ondforming reactionsi st hat they functiona sa na cyl electrophile to give the corresponding ketone (Scheme 1A).…”

“…[3,4] One striking aspect of using acyl fluorides in CÀCb ondforming reactionsi st hat they functiona sa na cyl electrophile to give the corresponding ketone (Scheme 1A). [5] Whenu sing these substrates in decarbonylative coupling reactions, biaryl compounds are obtainede fficiently (Scheme 1B). [6] Three-component coupling reactionso fa llenes or styrenes have also been reported, in whicht he acyl fluorides function as an acyl electrophile during the formationof the corresponding ketone (Scheme 1C).…”