Carbon dioxide (CO) is an available, abundant, and renewable C1 resource, which could be converted into value-added chemicals. Due to its inherent thermodynamic stability and kinetic inertness, it is difficult to realize its efficient utilization. Nevertheless, many elegant strategies for the utilization of CO have been developed using Lewis bases, frustrated Lewis pairs, hydroxyl-containing compounds, amino-group-containing compounds or transition metal catalysis. Among them, base-mediated carboxylation of -nucleophiles is an environmentally friendly strategy for CO conversion, which is operationally simple, using low-toxicity bases and economical available promoters, without the use of complex ligands or cocatalysts. This review summarizes related work on the base-mediated carboxylation of -nucleophiles with CO, based on the effects of nucleophiles, promoters, additives, and solvents. The types of pronucleophile are categorized as follows: hydrocarbon with C(sp)-H, C(sp)-H or C(sp)-H bonds, organosilanes, organotin, organoboron, and -tosylhydrazones. Typical mechanisms and applications of these carboxylation reactions are also depicted. Moreover, mechanistic comprehension of CO activation and conversion at a molecular level aims to further expand the repertoire of carboxylation transformations mediated by bases.
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http://dx.doi.org/10.1039/d3ob01367g | DOI Listing |
J Am Chem Soc
June 2024
Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States.
Per- and polyfluoroalkyl substances (PFAS) are persistent environmental pollutants linked to harmful health effects. Currently employed PFAS destruction methods are energy-intensive and often produce shorter-chain and recalcitrant partially fluorinated byproducts. We report the mineralization of five fluorotelomer compounds via a base-mediated degradation using NaOH and mild temperatures (120 °C) in a mixture of DMSO:HO (8:1 v/v).
View Article and Find Full Text PDFNat Commun
May 2024
Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon, 34141, South Korea.
In recent decades, strategies involving transition-metal catalyzed carbon-carbon or carbon-heteroatom bond coupling have emerged as potent synthetic tools for constructing intricate molecular architectures. Among these, decarboxylative carbon-nitrogen bond formation using abundant carboxylic acids or their derivatives has garnered notable attention for accessing alkyl- or arylamines, one of key pharmacophores. While several decarboxylative amination methods have been developed, the involvement of a common carboradical intermediate currently poses challenges in achieving stereospecific transformation toward chiral alkylamines.
View Article and Find Full Text PDFJ Org Chem
May 2024
Department of Chemistry, School of Natural Sciences, Shiv Nadar Institution of Eminence Deemed to be University, Dadri, Chithera, GB Nagar, Uttar Pradesh 201314, India.
By virtue of their high electrophilic nature, benzynes serve as reactive dienophiles in numerous cycloaddition reactions. However, in situ generation of benzyne involves either base-mediated thermal reactions, low-temperature conditions, or metal-catalyzed reactions of substituted arenes. This limits the applicability of benzynes as suitable dipolarophiles in cycloaddition reactions.
View Article and Find Full Text PDFOrg Biomol Chem
November 2023
Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China.
Carbon dioxide (CO) is an available, abundant, and renewable C1 resource, which could be converted into value-added chemicals. Due to its inherent thermodynamic stability and kinetic inertness, it is difficult to realize its efficient utilization. Nevertheless, many elegant strategies for the utilization of CO have been developed using Lewis bases, frustrated Lewis pairs, hydroxyl-containing compounds, amino-group-containing compounds or transition metal catalysis.
View Article and Find Full Text PDFAn efficient base-mediated/metal-free approach has been developed for the synthesis of 1-oxo-1,2,3,4-tetrahydropyrazino[1,2-]indole-3-carboxamide derivatives intramolecular indole N-H alkylation of novel bis-amide Ugi-adducts. In this protocol the Ugi reaction of ()-cinnamaldehyde derivatives, 2-chloroaniline, indole-2-carboxylic acid and different isocyanides was designed for the preparation of bis-amides. The main highlight of this study is the practical and highly regioselective preparation of new polycyclic functionalized pyrazino derivatives.
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