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Selective Enzymatic Oxidation of Silanes to Silanols
Author(s) -
Bähr Susanne,
BrinkmannChen Sabine,
GarciaBorràs Marc,
Roberts John M.,
Katsoulis Dimitris E.,
Houk K. N.,
Arnold Frances H.
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202002861
Subject(s) - chemistry , silanes , hydroxylation , silane , catalysis , organic chemistry , biotransformation , disiloxane , silanol , monooxygenase , cytochrome p450 , hydrogen atom abstraction , combinatorial chemistry , enzyme , stereochemistry , hydrogen
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.