Abstract
Simple petrochemical feedstocks are often the starting material for the synthesis of complex commodity and fine and specialty chemicals. Designing synthetic pathways for these complex and specific molecular structures with sufficient chemo-, regio-, enantio-, and diastereo-selectivity can expand the existing petrochemicals landscape. the two overarching challenges in designing such pathways are selective activation of chemically inert C-H bonds in hydrocarbons and systematic functionalization to synthesize complex structures. Multienzyme cascades are becoming a growing means of overcoming the first challenge. However, extending multienzyme cascade designs is restricted by the arsenal of enzymes currently at our disposal and the compatibility between specific enzymes. Here, we couple a bio electrocatalytic multienzyme cascade to organ catalysis, which are two distinctly different classes of catalysis, in a single system to address both challenges. based on the development and utilization of an anthraquinone (AQ)-Based redox polymer, the bio electrocatalytic step achieves regioselective terminal C-H bond oxy functionalization of chemically inert n-heptane. a second biocatalytic step selectively oxidizes the resulting 1-heptanol to heptanal. the succeeding inherently simple and durable l-proline-Based organ catalysis step is a complementary partner to the multienzyme steps to further functionalize heptanal to the corresponding α-hydrazino aldehyde. the "three-stage" streamlined design exerts much control over the chemical conversion, which renders the collective system a versatile and adaptable model for a broader substrate scope and more complex C-H functionalization.
Recommended Citation
N. S. Weliwatte et al., "Three-Stage Conversion of Chemically Inert N-Heptane to Α-Hydrazino Aldehyde based on Bioelectrocatalytic C-H Bond Oxyfunctionalization," ACS Catalysis, vol. 13, no. 1, pp. 563 - 572, American Chemical Society, Jan 2023.
The definitive version is available at https://doi.org/10.1021/acscatal.2c04003
Department(s)
Chemistry
Publication Status
Open Access
Keywords and Phrases
C-H activation; hybrid bioelectrocatalysis; in vitro multienzyme cascade; organocatalysis; redox polymer-mediated; tandem catalysis
International Standard Serial Number (ISSN)
2155-5435
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2025 American Chemical Society, All rights reserved.
Publication Date
06 Jan 2023
Comments
National Science Foundation, Grant CHE2002158