Nickel‐Catalyzed CO₂ Rearrangement of Enol Metal Carbonates for the Efficient Synthesis of β‐Ketocarboxylic Acids

Abstract

4-Methylene-1,3-dioxolan-2-ones underwent oxidative addition of a Ni catalyst in the presence of Me Al(OMe), followed by a coupling reaction with alkynes, to form δ,ϵ-unsaturated β-ketocarboxylic acids with high regio- and stereoselectivity. The reaction proceeds by [1,3] rearrangement of an enol metal carbonate intermediate and the formal reinsertion of CO .

Catalytic Transformations of Functionalized Cyclic Organic Carbonates

“…The presence of Me 2 Al(OMe) is crucial toward the selective formation of β‐keto‐carboxylic acids, and other organometallic reagents such as Me 3 B and Me 2 Zn proved to be less efficient. An eight‐membered nickelacycle was proposed to be the key intermediate in this process …”

A Noble‐Metal‐Free Metal–Organic Framework (MOF) Catalyst for the Highly Efficient Conversion of CO2 with Propargylic Alcohols

“…As a result, much effort has been devoted to developing effective methods to chemical fixation of CO 2 , mainly including the cycloaddition of epoxides or aziridines with CO 2 , and carboxylation of terminal alkyne molecules with CO 2 . Recently, the cyclization of propargylic alcohols with CO 2 has also aroused intense interest, because the resultant products α‐alkylidene cyclic carbonates are a class of important heterocyclic compounds in nature products synthesis, pharmaceutical chemistry, and polymers, such as β‐ketocarboxylic acids, nitropyrrolins A–E, 2‐cyclopentenones, poly(urethane)s and poly(carbonate)s . However, owing to the thermodynamic stability of C=O bond (bond enthalpy +805 kJ mol −1 ) and stable electronic structure of in CO 2 , highly active catalysts are often needed in promoting this cyclization reaction, like Ag nanoparticles, Ag salts, and Ag‐MOF or nanoparticle Ag@MOFs, and it should be noted that most of these catalysts are associated with noble metal Ag.…”

Highly Efficient Fixation of Carbon Dioxide at RT and Atmospheric Pressure Conditions: Influence of Polar Functionality on Selective Capture and Conversion of CO2

“…Hence, extensive research efforts are being made worldwide to mitigate the increasing concentration of CO 2 through selective capture and subsequent conversion to value-added chemicals or fuels. − However, the carbon dioxide being thermodynamically stable (bond enthalpy of +805 kJ/mol) and kinetically inert requires high temperature and pressure conditions for its activation. − In this regard, it is highly desirable to develop efficient catalysts that can selectively capture and convert CO 2 into value-added chemicals under mild conditions. Toward this direction, several strategies have been developed for the conversion of CO 2 into various high-value chemicals. − Among them, the cyclic carboxylation of propargylic alcohols with CO 2 to generate α-alkylidene cyclic carbonates has attracted significant interest owing to their possible applications in the synthesis of plastics, natural products and polymers, beta-keto carboxylic acids, polycarbonates and polyurethanes, cyclopentenones, and so on. Further, the synthesis of oxazolidinones, an important building blocks of antibiotics by a tandem reaction between propargylic alcohols, CO 2 , and primary amines, has attracted considerable interest of green chemistry researchers .…”

“…Toward this direction, several strategies have been developed for the conversion of CO 2 into various high-value chemicals. 8−16 Among them, the cyclic carboxylation of propargylic alcohols with CO 2 to generate α-alkylidene cyclic carbonates has attracted significant interest owing to their possible applications in the synthesis of plastics, 17 natural products and polymers, 18 beta-keto carboxylic acids, 19 polycarbonates and polyurethanes, 20 cyclopentenones, 21 and so on. Further, the synthesis of oxazolidinones, an important building blocks of antibiotics by a tandem reaction between propargylic alcohols, CO 2 , and primary amines, has attracted considerable interest of green chemistry researchers.…”