ChemRxiv
These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
1/1
0/0

Selective Enzymatic Oxidation of Silanes to Silanols

preprint
submitted on 17.03.2020 and posted on 18.03.2020 by Susanne Bähr, Sabine Brinkmann-Chen, Marc Garcia-Borràs, John M Roberts, Dimitris E. Katsoulis, Kendall N Houk, Frances H. Arnold
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 (P450BM3 from Bacillus megaterium, CYP102A1) has promiscuous activity for oxidation of hydrosilanes to make silanols. Directed evolution enhanced this non-native activity and created a highly efficient catalyst for selective silane oxidation under mild conditions with oxygen as terminal oxidant. The evolved enzyme does not touch C–H bonds also present in the silane substrates, nor does this biotransformation 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 P450’s native C–H hydroxylation mechanism. Enzymatic silane oxidation now extends Nature’s already impressive catalytic repertoire.

Read the published paper

in Angewandte Chemie International Edition

Logo branding

Categories

History

Email Address of Submitting Author

sabine@cheme.caltech.edu

Institution

California Institute of Technology

Country

USA

ORCID For Submitting Author

0000-0002-5419-4192

Declaration of Conflict of Interest

JM Roberts and DE Katsoulis are employed by the Dow Chemical Company

Exports

Read the published paper

in Angewandte Chemie International Edition

Logo branding

Categories

Exports