Cooperative chemoenzymatic approaches to transforming CO2 into high-value products

Abstract

Cooperative chemoenzymatic catalysis, combining the strengths of chemical and enzymatic reactions, has emerged as a powerful strategy for advancing innovative biomanufacturing platforms leveraging CO₂ as a feedstock. This approach enables the synthesis of value-added molecules and materials from abundant low-carbon resources. In this review, we first highlight the critical role that chemoenzymatic reactions play in prebiotic chemistry, offering valuable insights into the design of complex biomolecules from simple precursors. We then examine the opportunities within chemoenzymatic synthesis through prominent examples: the ancient formose reaction followed by biotransformation, the electrochemical conversion of CO₂ into energetic C1 and C2 compounds with subsequent enzymatic conversions for producing long carbon-chain products, the regeneration of energetic molecules such as ATP and NAD(P)H cofactors, and the integration of chemoenzymatic reactions in carbon-chain elongation and downstream purification processes. This synergistic approach not only maximizes the utility of CO₂ as a feedstock but also contributes to the development of sustainable and efficient methods for CO₂ utilization, advancing the fields of green chemistry and sustainable industrial practices.