Transition‐Metal‐Catalyzed Decarbonylative Coupling Reactions: Concepts, Classifications, and Applications

Abstract

Transition metal-catalyzed decarbonylative coupling reactions have emerged as a powerful alternative to conventional cross-coupling protocols due to the advantages associated with the use of carbonyl-containing functionalities as coupling electrophiles instead of commonly used organohalides or sulfates. A wide variety of novel transformations based on this concept have been successfully achieved, including decarbonylative carbon-carbon and carbon-heteroatom bond forming reactions. In this Review, we summarize the recent progress in this field and present a comprehensive overview of metal-catalyzed decarbonylative coupling reactions with carbonyl derivatives.

Alkyl Carbon–Carbon Bond Formation by Nickel/Photoredox Cross‐Coupling

“…Thea bility of organonickel intermediates to engage acyl electrophiles in oxidative addition has been reported. [74] Building on this work, Ni/photoredox dual catalysis was employed to couple numerous acyl electrophiles with alkyl radical precursors.A satestament to the modularity of the catalytic system, multiple classes of both acyl electrophiles (acylchlorides, [75] acyl imides, [76] anhydrides, [77] isocyanates, [78] and thioesters [77d] )and radical precursors have been engaged within the reaction manifold. Achieving selective acyl transfer when using mixed anhydrides can prove challenging because of the presence of two C(sp 2 ) À Ob onds that must be differentiated by the Ni-catalyst.…”

Synthesis of Arylstannanes via Palladium‐Catalyzed Decarbonylative Coupling of Aroyl Fluorides

“…The transformation of carboxylic acids or their derivatives through an efficient and selective activation is an attractive topic. [1] Acyl fluorides, the stable and readily accessible carboxylic acid derivatives, are traditionally used as acylation reagents via nucleophilic substitution or transition-metal (TM) catalyzed cross-coupling reaction. [2] Recently, TM-catalyzed decarbonylative reactions of aroyl fluorides have been successfully realized for a number of transformations, including trifluoromethylation, [3] Suzuki-Miyaura type arylation, [4] reduction, [5] alkylation [6] and direct CÀ H arylation [7] (Scheme 1a).…”

Alkyl‐C‐C‐Bindungsbildung durch Nickel/Photoredox‐Kreuzkupplung

“…[74] Aufd ieser Grundlage wurde die duale Ni/ Photoredox-Katalyse zur Kupplung zahlreicher Acyl-Elektrophile mit Alkylradikalvorstufen eingesetzt. [74] Aufd ieser Grundlage wurde die duale Ni/ Photoredox-Katalyse zur Kupplung zahlreicher Acyl-Elektrophile mit Alkylradikalvorstufen eingesetzt.…”

“…Die Reaktivitätv on Organonickelintermediaten mit Acyl-Elektrophilen in oxidativen Additionsreaktionen wurde beschrieben. [74] Aufd ieser Grundlage wurde die duale Ni/ Photoredox-Katalyse zur Kupplung zahlreicher Acyl-Elektrophile mit Alkylradikalvorstufen eingesetzt. Als Beleg für den modularen Aufbau des Katalysesystems wurden mehrere Klassen von sowohl Acyl-Elektrophilen (Acylchloriden, [75] Acylimiden, [76] Anhydriden, [77] Isocyanaten [78] und Thioestern [77d] )a ls auch Radikalvorstufen in der Reaktion verwendet.…”