Pick, Lisa, Oehme, Vivien, Hartmann, Julia et al. (4 more authors) (2024) SilE-R and SilE-S - DABB Proteins Catalyzing Enantiospecific Hydrolysis of Organosilyl Ethers. Angewandte Chemie International Edition. ISSN 1433-7851
Abstract
Silyl ethers fulfil a fundamental role in synthetic organic chemistry as protecting groups and their selective cleavage is an important factor in their application. We present here for the first time two enzymes, SilE-R and SilE-S, which are able to hydrolyze silyl ethers. They belong to the stress-response A/B barrel domain (DABB) family and are able to cleave the Si-O bond with opposite enantiopreference. Silyl ethers containing aromatic, cyclic or aliphatic alcohols and, depending on the alcohol moiety, silyl functions as large as TBDMS are accepted. The X-ray crystal structure of SilE-R, determined to a resolution of 1.98 Ȧ, in combination with mutational studies, revealed an active site featuring two histidine residues, H8 and H79, which likely act synergistically as nucleophile and Brønsted base in the hydrolytic mechanism, which has not previously been described for enzymes. Although the natural function of SilE-R and SilE-S is unknown, we propose that these ‘silyl etherases’ may have significant potential for synthetic applications.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2024 The Authors. |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Funding Information: | Funder Grant number BBSRC (BIOTECHNOLOGY AND BIOLOGICAL SCIENCES RESEARCH COUNCIL) BB/T017805/1 |
Depositing User: | Pure (York) |
Date Deposited: | 23 May 2024 14:40 |
Last Modified: | 07 Jan 2025 12:10 |
Published Version: | https://doi.org/10.1002/anie.202404105 |
Status: | Published online |
Refereed: | Yes |
Identification Number: | 10.1002/anie.202404105 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:212759 |
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Description: Angew Chem Int Ed - 2024 - Pick - SilE‐R and SilE‐S DABB Proteins Catalying Enantiospecific Hydrolysis of Organosilyl
Licence: CC-BY 2.5