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Selective Enzymatic Oxidation of Silanes to Silanols

Bähr, Susanne and Brinkmann-Chen, Sabine and Garcia-Borràs, Marc and Roberts, John M. and Katsoulis, Dimitris E. and Houk, Kendall N. and Arnold, Frances H. (2020) Selective Enzymatic Oxidation of Silanes to Silanols. Angewandte Chemie International Edition, 59 (36). pp. 15507-15511. ISSN 1433-7851. PMCID PMC7511438. https://resolver.caltech.edu/CaltechAUTHORS:20200318-093621776

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Abstract

Compared to the biological world's rich chemistry for functionalizing carbon, enzymatic transformations of the heavier homologue silicon are rare. We report that a wild‐type cytochrome P450 monooxygenase (P450_(BM3) from Bacillus megaterium, CYP102A1) has promiscuous activity for oxidation of hydrosilanes to give silanols. Directed evolution was applied to enhance this non‐native activity and create a highly efficient catalyst for selective silane oxidation under mild conditions with oxygen as the terminal oxidant. The evolved enzyme leaves C−H bonds present in the silane substrates untouched, and this biotransformation does not lead to disiloxane formation, a common problem in silanol syntheses. Computational studies reveal that catalysis proceeds through hydrogen atom abstraction followed by radical rebound, as observed in the native C−H hydroxylation mechanism of the P450 enzyme. This enzymatic silane oxidation extends nature's impressive catalytic repertoire.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1002/anie.202002861DOIArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7511438/PubMed CentralArticle
https://doi.org/10.26434/chemrxiv.11996379.v1DOIDiscussion Paper
ORCID:
AuthorORCID
Bähr, Susanne0000-0001-5113-7646
Brinkmann-Chen, Sabine0000-0002-5419-4192
Garcia-Borràs, Marc0000-0001-9458-1114
Roberts, John M.0000-0001-7733-6301
Houk, Kendall N.0000-0002-8387-5261
Arnold, Frances H.0000-0002-4027-364X
Additional Information:© 2020 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim. Manuscript received: February 24, 2020; Accepted manuscript online: March 24, 2020; Version of record online: April 21, 2020. This work was supported by the Dow University Partnership Initiative(227027AO),the Rothenberg Innovation Initiative (RI2) Program (F.H.A.), the NIH National Institute for General Medical Sciences GM-124480 (K.N.H.), the Deutsche Forschungsgemeinschaft (DFG) Postdoctoral Fellowship (BA 6604/1-1 to S.B.), and the Spanish MINECO (JdC-I contract IJCI-2017-33411 to M.G.-B.). We thank N. W. Goldberg, Dr. S. B. J. Kan, and A. M. Knight for productive discussions, and Dr. Zhijun Jia for experimental assistance.
Funders:
Funding AgencyGrant Number
Dow Chemical Company227027AO
Rothenberg Innovation Initiative (RI2)UNSPECIFIED
NIHGM-124480
Deutsche Forschungsgemeinschaft (DFG)BA 6604/1-1
Ministerio de Economía, Industria y Competitividad (MINECO)IJCI-2017-33411
Subject Keywords:biocatalysis; directed evolution; monooxygenation; P450 enzymes; silanols
Issue or Number:36
PubMed Central ID:PMC7511438
Record Number:CaltechAUTHORS:20200318-093621776
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200318-093621776
Official Citation:S. Bähr, S. Brinkmann-Chen, M. Garcia-Borràs, J. M. Roberts, D. E. Katsoulis, K. N. Houk, F. H. Arnold, Angew. Chem. Int. Ed. 2020, 59, 15507
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:101963
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:18 Mar 2020 16:55
Last Modified:09 Feb 2022 00:50

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