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3.2.3.2 Carbonylation and Alkenylation

DOI: 10.1055/sos-SD-209-00407

Kalyani, D.; Desai, L. V.Science of Synthesis: Cross Coupling and Heck-Type Reactions, (20133752.

The preceding sections detailed transformations involving the coupling of sp3 C—H bonds with arylating reagents. Examples of palladium-catalyzed carbonylation and alkenylations of unactivated sp3 C—H bonds have also been developed as alternative methods to construct C(sp3)—C bonds. Early reports by Fujiwara demonstrated the first examples of the palladium-catalyzed C(sp3)—H carbonylation of alkanes.[‌93‌‌95‌] The carbonylation of simple alkanes, such as ethane, is achieved using a palladium(II) acetate/copper(II) acetate dual catalyst system under a carbon monoxide atmosphere (20–50 atm) with potassium persulfate as the terminal oxidant and trifluoroacetic acid as the solvent. Although the carboxylic acid products of this transformation are efficiently obtained, these reactions are limited by the use of excess substrate and high carbon monoxide pressures (Scheme 37).

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References