Synthesis of Vinyl Carboxylic Acids using Carbon Dioxide as a Carbon Source by Iron‐Catalyzed Hydromagnesiation

Abstract

An iron‐catalyzed synthesis of α,β‐unsaturated carboxylic acids from alkynes and carbon dioxide was developed. This reaction proceeds through hydromagnesiation of alkynes followed by carbon dioxide insertion under atmospheric pressure and ambient temperature in the presence of iron and a Grignard reagent as a catalyst and hydride source, respectively. Several symmetrical and unsymmetrical alkynes were transformed into the corresponding acids in good to excellent yields. The methodology provides an efficient route to the synthesis of vinyl carboxylic acids.

Hydroelementation of diynes

“…iron complexes. [88][89][90][91][92][93][94][95] Hydromagnesation of conjugated and separated diynes was reported only by Nakamura et al, who synthesised alkenylmagnesium compounds using EtMgBr 2 as a hydrogen source and FeCl 2 3 as a catalyst. 96 The reaction occurred with 1,2-diarylalkynes and 1,3-diynes 1a-e with high (Z)-selectivity, in short reaction time (15 min), at room temperature.…”

“…This comprehensive review will be helpful for all advanced researchers and newcomers working on the synthesis of organometallic compounds and their further applications in organic chemistry, synthesis of natural compounds, pharmaceuticals, with the emphasis placed on the process regio-and iron complexes. [88][89][90][91][92][93][94][95] Hydromagnesation of conjugated and separated diynes was reported only by Nakamura et al, who synthesised alkenylmagnesium compounds using EtMgBr 2 as a hydrogen source and FeCl 2 3 as a catalyst. 96 The reaction occurred with 1,2-diarylalkynes and 1,3-diynes 1a-e with high (Z)-selectivity, in short reaction time (15 min), at room temperature.…”

Pd Nanoparticles Decorated on Hypercrosslinked Microporous Polymer: A Highly Efficient Catalyst for the Formylation of Amines through Carbon Dioxide Fixation

“…Substitution of hazardous and toxic carbon monoxide as a C1 source with carbon dioxide is a greener and sustainable move towards the production of various important carbonyl group containing chemicals . To date, a wide range of methodologies have been developed for carbon dioxide fixation such as carboxylation of aryl halides/alkynes, formylation of aryl halides, formylation of amines, methylation of amines, and cyclization with epoxides or aziridines . Formylation of amines by using carbon dioxide as the C1 source is a very useful reaction as most of the N‐formylated products are used as intermediates for various agrochemicals, fragrances, drugs, and dyes .…”

Access to Substituted Propenoic Acids via Rh(III)-Catalyzed C–H Allylation of (Hetero)Arenes with Methyleneoxetanones

“…Consequently, a large number of methods have been established to access acrylic acids. For example, Reppe, Alper, and others realized catalytic hydrocarboxylation of alkynes with CO, HCOOH, and CO 2 as a C1 source (Scheme ). However, these methods often suffer from high pressure, a stoichiometric amount of organometallic reagent or metal reductant, and poor functional group tolerance with the employment of sensitive reagents.…”