Abstract
In this chapter, we have developed a protocol that using formic acid as C1 source to directly carboxylate allylic alcohols in the presence of a low loading of palladium catalyst and acetic anhydride as additive, affording β, γ-unsaturated carboxylic acids with excellent chemo-, regio-, and stereoselectivity. The reaction proceeds through a carbonylation process with in situ-generated carbon monoxide under mild conditions, avoiding the use of high-pressure gaseous CO. A bisphosphine ligand with a large bite angle (4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, xantphos) was found to be uniquely effective for this transformation. The regio- and stereoconvergence of this reaction is ascribed to the thermodynamically favored isomerization of the allylic electrophile in the presence of the palladium catalyst.
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Fu, MC. (2020). Efficient Pd-Catalyzed Regio- and Stereoselective Carboxylation of Allylic Alcohols with Formic Acid. In: Studies on Green Synthetic Reactions Based on Formic Acid from Biomass. Springer Theses. Springer, Singapore. https://doi.org/10.1007/978-981-15-7623-2_4
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DOI: https://doi.org/10.1007/978-981-15-7623-2_4
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