Regioselective Ni-Catalyzed Carboxylation of Allylic and Propargylic Alcohols with Carbon Dioxide

Abstract

An efficient Ni-catalyzed reductive carboxylation of allylic alcohols with CO has been successfully developed, providing linear β,γ-unsaturated carboxylic acids as the sole regioisomer with generally high E/Z stereoselectivity. In addition, the carboxylic acids can be generated from propargylic alcohols via hydrogenation to give allylic alcohol intermediates, followed by carboxylation. A preliminary mechanistic investigation suggests that the hydrogenation step is made possible by a Ni hydride intermediate produced by a hydrogen atom transfer from water.

Carboxylation Reactions Using Carbon Dioxide as the C1 Source via Catalytically Generated Allyl Metal Intermediates

“…Mei also reported that a Ni complex catalyzed the carboxylation of allyl alcohols using manganese as a reducing agent (Scheme 8, Chen et al, 2017). This reaction proceeded in the presence of an Ni complex with a neocuproine ligand in N.N-dimethylformamide (DMF) at room temperature under 1 atm of CO 2 .…”

Nickel-Catalyzed Reductive Cross-Couplings: New Opportunities for Carbon–Carbon Bond Formations through Photochemistry and Electrochemistry

“…Under nickel/Mn or Zn conditions, aryl and vinyl triflates, benzyl, alkyl pseudo-electrophiles, alkenyl and alkynyl compounds have been utilized for the synthesis of various carboxylates. [129][130][131][132][133][134][135][136][137][138][139][140][141] Notably, nickel-catalyzed reductive migratory cross-coupling of alkyl bromides with CO 2 was also realized by Martin and co-workers 142 (Scheme 16b). Recently, König and co-workers 143 leveraged a nickel/photoredox dual catalysis for the reductive carboxylation of aryl and alkyl bromides/triflates (Scheme 16c).…”

Recent Advances in the Catalytic Umpolung Carboxylation of Allylic Alcohol Derivatives with Carbon Dioxide

“…After a detailed investigation of the nickel source and ligand, the combination of Ni(acac) 2 and the neocuproine ligand (L2) proved to be effective for promoting linear-selective carboxylation (Figure 6, top). [16] Under mild conditions, an array of linear β,γ-unsaturated carboxylic acids were produced in moderate to high yields, and the configuration of the alkene moiety in the linear products was dominantly the E-form. The reaction was initiated by the oxidative addition of the allyl alcohol to Ni(0) generated in situ via the reduction of Ni(II) with Mn, delivering the π-allyl Ni(II) species.…”