Dataset Information

Milled Dry Ice as a C1 Source for the Carboxylation of Aryl Halides.

ABSTRACT: The use of carbon dioxide as a C1 chemical feedstock remains an active field of research. Here we showcase the use of milled dry ice as a method to promote the availability of CO₂ in a reaction solution, permitting practical synthesis of arylcarboxylic acids. Notably, the use of milled dry ice produces marked increases in yields relative to those obtained with gaseous CO₂, as previously reported in the literature.

SUBMITTER: O'Brien CJ

PROVIDER: S-EPMC9477210 | biostudies-literature | 2021 May

REPOSITORIES: biostudies-literature

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Milled Dry Ice as a C1 Source for the Carboxylation of Aryl Halides.

O'Brien Connor J CJ Nicewicz David A DA

Synlett : accounts and rapid communications in synthetic organic chemistry 20210204 8

The use of carbon dioxide as a C1 chemical feedstock remains an active field of research. Here we showcase the use of milled dry ice as a method to promote the availability of CO<sub>2</sub> in a reaction solution, permitting practical synthesis of arylcarboxylic acids. Notably, the use of milled dry ice produces marked increases in yields relative to those obtained with gaseous CO<sub>2</sub>, as previously reported in the literature. ...[more]

PMID: 36120490

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Project description:The nickel-catalyzed carboxylation of organic halides or pseudohalides using carbon dioxide is an emerging method to prepare synthetically valuable carboxylic acids. Here, we report a detailed mechanistic investigation of these reactions using the carboxylation of aryl halides with (PPh3)2NiIICl2 as a model reaction. Our studies allow us to understand several general features of nickel-catalyzed carboxylation reactions. For example, we demonstrate that both a Lewis acid and halide source are beneficial for catalysis. To this end, we establish that heterogeneous Mn(0) and Zn(0) reductants are multifaceted reagents that generate noninnocent Mn(II) or Zn(II) Lewis acids upon oxidation. In a key result, a rare example of a well-defined nickel(I) aryl complex is isolated, and it is demonstrated that its reaction with carbon dioxide results in the formation of a carboxylic acid in high yield (after workup). The carbon dioxide insertion product undergoes rapid decomposition, which ca These three oxidation states correspond to the onbe circumvented by a ligand metathesis reaction with a halide source. Our studies have led to both a revised mechanism and the development of a broadly applicable strategy to improve reductive carboxylation reactions. A critical component of this strategy is that we have replaced the heterogeneous Mn(0) reductant typically used in catalysis with a well-defined homogeneous organic reductant. Through its use, we have increased the range of ancillary ligands, additives, and substrates that are compatible with the reaction. This has enabled us to perform reductive carboxylations at low catalyst loadings. Additionally, we demonstrate that reductive carboxylations of organic (pseudo)halides can be achieved in high yields in more practically useful, non-amide solvents. Our results describe a mechanistically guided strategy to improve reductive carboxylations through the use of a homogeneous organic reductant, which may be broadly translatable to a wide range of cross-electrophile coupling reactions.

Dataset Information

Milled Dry Ice as a C1 Source for the Carboxylation of Aryl Halides.

Publications

Milled Dry Ice as a C1 Source for the Carboxylation of Aryl Halides.

Similar Datasets

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