Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
Review
. 2019 Jun 27:7:430.
doi: 10.3389/fchem.2019.00430. eCollection 2019.

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

Tetsuaki Fujihara  1 , Yasushi Tsuji  1
Affiliations
Review

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

Tetsuaki Fujihara et al. Front Chem. .

Abstract

The use of carbon dioxide (CO2) is an important issue with regard to current climate research and the Earth's environment. Transition metal-catalyzed carboxylation reactions using CO2 are highly attractive. This review summarizes the transition metal-catalyzed carboxylation reactions of organic substrates with CO2 via allyl metal intermediates. First, carboxylation reactions via transmetalation are reviewed. Second, catalytic carboxylation reactions using allyl electrophiles and suitable reducing agents are summarized. The last section discusses the catalytic carboxylation reactions via addition reactions, affording allyl metal intermediates.

Keywords: addition reactions; allyl metals; carbon dioxide; carboxylic acids; oxidative addition; transmetalation.

PubMed Disclaimer

Figures

Scheme 1
Scheme 1
Generation of allyl metal intermediates: (A) transmetalation, (B) oxidative addition, and (C) addition reaction.
Scheme 2
Scheme 2
Catalytic carboxylation of allylstannane with CO2 using a Pd complex: (A) the reaction reported by Shi and Nicholas (1997) (B) the reaction reported by Johansson and Wendt (2007).
Scheme 3
Scheme 3
Catalytic carboxylation of allylstannane with CO2 using a Pd complex.
Scheme 4
Scheme 4
Cu-catalyzed carboxylation of allylboronates with CO2.
Scheme 5
Scheme 5
Pd-catalyzed carboxylation of cinnamyl acetate with CO2 under electrolysis.
Scheme 6
Scheme 6
Ni-catalyzed ligand-controlled regiodivergent carboxylation of allyl acetates with CO2.
Scheme 7
Scheme 7
Pd-catalyzed carboxylation of allyl alcohols with CO2 using Et2Zn.
Scheme 8
Scheme 8
Ni-catalyzed carboxylation of allyl alcohols with CO2 using a manganese as reducing agent.
Scheme 9
Scheme 9
Pd-catalyzed carboxylative coupling of benzyl chlorides and an allylstannane under CO2.
Scheme 10
Scheme 10
Co-catalyzed allylic C-H carboxylation of allylarenes and a proposed mechanism.
Scheme 11
Scheme 11
Pd-catalyzed hydrocarboxylation of 1,2-dienes and a proposed mechanism.
Scheme 12
Scheme 12
Cu-catalyzed enantioselective hydrohydroxymethylation of 1,2-dienes using a hydrosilane and CO2 and a proposed mechanism.
Scheme 13
Scheme 13
Cu-catalyzed hydrocarboxylation of 1,2-dienes.
Scheme 14
Scheme 14
Cu-catalyzed enantioselective hydrohydroxymethylation of 1,3-dienes using a hydrosilane and CO2.
Scheme 15
Scheme 15
Cu-catalyzed silacarboxylation of 1,2-dienes and a proposed mechanism.
See this image and copyright information in PMC

References

    1. Aresta M., Dibenedetto A., Angelini A. (2014). Catalysis for the valorization of exhaust carbon: from CO2 to chemicals, materials, and fuels. Technological use of CO2. Chem. Rev. 114, 1709–1742. 10.1021/cr4002758 - DOI - PubMed
    1. Artz J., Mueller T. E., Thenert K., Kleinekorte J., Meys R. L., Sternberg A., et al. . (2018). Sustainable conversion of carbon dioxide: an integrated review of catalysis and life cycle assessment. Chem. Rev. 118, 434–504. 10.1021/acs.chemrev.7b00435 - DOI - PubMed
    1. Borjesson M., Moragas T., Gallego D., Martin R. (2016). Metal-catalyzed carboxylation of organic (Pseudo)halides with CO2. ACS Catal. 6, 6739–6749. 10.1021/acscatal.6b02124 - DOI - PMC - PubMed
    1. Cai X., Xie B. (2013). Carboxylative reactions for the transformation of carbon dioxide into carboxylic acids and derivatives. Synthesis 45, 3305–3324. 10.1055/s-0033-1340061 - DOI
    1. Chen X.-G., Xu X.-T., Zhang K., Li Y.-Q., Zhang L.-P., Fang P., et al. (2018). Transition-metal-catalyzed carboxylation of organic halides andtheir surrogates with carbon dioxide. Synthesis 50, 35–48. 10.1055/s-0036-1590908 - DOI

LinkOut - more resources