Aldehyde Carboxylation: A Concise DFT Mechanistic Study and a Hypothetical Role of CO2 in the Origin of Life

Martin Juhl; Myungjo J. Kim; Hee-Yoon Lee; Mu-Hyun Baik; Ji-Woong Lee

doi:10.1055/s-0037-1611738

Synlett, Table of Contents

Synlett 2019; 30(09): 987-996
DOI: 10.1055/s-0037-1611738

synpacts

Aldehyde Carboxylation: A Concise DFT Mechanistic Study and a Hypothetical Role of CO₂ in the Origin of Life

Martin Juhl

^aDepartment of Chemistry, Nano-Science Center, University of Copenhagen, Universitetsparken 5, Copenhagen Ø, 2100, Denmark Email: jiwoong.lee@chem.ku.dk

,

Myungjo J. Kim

^bDepartment of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of Korea

^cCenter for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon 34141, Republic of Korea

,

Hee-Yoon Lee *

^bDepartment of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of Korea

,

Mu-Hyun Baik *

^bDepartment of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of Korea

^cCenter for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon 34141, Republic of Korea

,

Ji-Woong Lee *

^aDepartment of Chemistry, Nano-Science Center, University of Copenhagen, Universitetsparken 5, Copenhagen Ø, 2100, Denmark Email: jiwoong.lee@chem.ku.dk

› Author Affiliations

Abstract

All articles of this category

^# These authors contributed equally

Abstract

Carbon dioxide is arguably one of the most stable carbon-based molecules, yet enzymatic carbon fixation processes enabled the sustainable life cycle on Earth. Chemical reactions involving CO₂-functionalization often suffer from low efficiency with highly reactive substrates. We recently reported mild carboxylation of aldehydes to furnish α-keto acids – a building block for chiral α-amino acids via reductive amination. Here, we discuss potential reaction mechanisms of aldehyde carboxylation reactions based on two promoters: NHCs and KCN in the carboxylation reaction. New DFT mechanistic studies suggested a lower reaction barrier for a CO₂-functionalization step, implying a potential role of CO₂ in prebiotic evolution of organic molecules in the primordial soup.

1 Introduction: Aldehydes, Benzoins, Carboxylic Acids

2 CO₂-Activation: NHC, Cyanide, Lewis Acid and Water

3 A Breslow Intermediate: Benzoin Reaction vs. Carboxylation with CO₂

4 Carboxylation in the Primordial Soup

5 Conclusion

Key words

carbon dioxide - umpolung - origin of life - cyanide - amino acids

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References

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