Title: Photobiocatalysis for Abiological Transformations

Abstract

Harnessing biocatalysts for novel abiological transformations is a longstanding goal of synthetic chemistry. Combining the merits of biocatalysis and photocatalysis allows for selective transformations fueled by visible light and offers many advantages including new reactivity, high enantioselectivity, greener syntheses, and high yields. Photoinduced electron or energy transfer enables synthetic methodologies that complement conventional two electron processes or offer orthogonal pathways for developing new reactions. Enzymes are well suited and can be tuned by directed evolution to exert control over radical intermediates thereby suppressing undesirable reactions and delivering high chemo- and stereoselectivities. Within the past decade, the combination of biocatalysis and photocatalysis was mainly focused on exploiting light-regenerated cofactors to increase native enzymatic activity. However, recent developments have demonstrated that the combination can unlock new-to-nature chemistry. Particularly, the discovery and application of new strategies are well poised to expand the applications of photobiocatalysis. In the past three years, our lab has been studying the combinations of photocatalysis and biocatalysis which can be applied to create new synthetic methodologies and solve challenges in synthetic organic chemistry. Our efforts have expanded the strategies for combining external photocatalysts with enzymes through the construction of a synergistic cooperative stereoconvergent reduction system consisting of photosensitized energymore » transfer and ene-reductase catalyzed alkene reduction. Additionally, our efforts have also extended the capability of cofactor-dependent photoenzymatic systems to include enantioselective bimolecular radical hydroalkylations of alkenes by irradiating electron donor-acceptor complexes comprised of enzymatic redox active cofactors and unnatural substrates. In this Account, we highlight strategies developed by our group and others for combining biocatalysis and photocatalysis with the aim of introducing nonnatural reactivity to enzymes. Presently, strategies applied to achieve this goal include the repurposing of newly discovered photoactive enzymes, the elucidation of new photoreactivity within cofactor-dependent enzymes, the combination of external photocatalysts with enzymes, and the construction of artificial photoenzymes. By demonstrating the successful application of these strategies for achieving selective new-to-nature transformations, we hope to spur interest in the expanding the scope of photobiocatalytic systems through the use and extension of these strategies and creation of new strategies. In addition, we hope to elucidate the intuition in synergizing the unique capabilities of biocatalysis and photocatalysis so that photobiocatalysis can be recognized as a potential solution to difficult challenges in synthetic organic chemistry.« less

Authors:

Harrison, Wesley ^[1]; Huang, Xiaoqiang  ^[1];

• Search DOE PAGES for author "Huang, Xiaoqiang"
• Search DOE PAGES for ORCID "0000-0002-0927-4812"

Zhao, Huimin  ^[1]

• Search DOE PAGES for author "Zhao, Huimin"
• Search DOE PAGES for ORCID "0000-0002-9069-6739"

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1. Univ. of Illinois at Urbana-Champaign, IL (United States)

Publication Date:

Wed Mar 30 00:00:00 EDT 2022

Research Org.:

Univ. of Illinois at Urbana-Champaign, IL (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Biological and Environmental Research (BER)

OSTI Identifier:

1902721

Grant/Contract Number:  

SC0018420

Resource Type:

Accepted Manuscript

Journal Name:

Accounts of Chemical Research

Additional Journal Information:

Journal Volume: 55; Journal Issue: 8; Journal ID: ISSN 0001-4842

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Electromagnetic radiation; Peptides and proteins; Photocatalysis; Photocatalysts; Redox reactions