Chiral Auxiliaries as Docking/Protecting Groups in Biohydroxylation:(S)‐Specific Hydroxylation of Enantiopure tert‐Butyl‐Substituted Spirooxazolidines Derived From Cyclopentanone

Abstract

An enantiopure tert-butyl-substituted derivative of cyclopentanone, which is a vital member of the chiral docking/ protecting group series, is employed, for the first time, to stereoselectively (90 % de) introduce an (S)-configured hydroxyl group onto an unactivated carbon atom present in the cyclo-

Enzyme-mediated oxidations for the chemist

“…621 Furthermore, variants converting This journal is © The Royal Society of Chemistry 2011 In addition to these protein engineering approaches, substrate engineering following the so-called docking/protecting group concept has also been reported for selective C-H bond hydroxylations. [627][628][629][630][631][632] The concept is based on the reversible covalent modification of the substrate of interest with a docking/protection group. In the reported cases, substrates that were either not converted at all or underwent significant side reactions could be selectively hydroxylated in vivo.…”

Specific 5-Hydroxylation of Piperlongumine byBeauveria bassianaATCC 7159

“…Stereoselective hydroxylation of unactivated carbon atoms is generally a very daunting task in modern synthetic chemistry. 18) In this work, the substrate was efficiently (100%) hydroxylated by B. bassiana. This new hydroxyl group can then be used to introduce other functional groups for further structural optimization.…”

The taming of oxygen: biocatalytic oxyfunctionalisations

“…182 Next to protein engineering 20,158,164,[183][184][185][186][187][188][189] also substrate engineering may be a promising approach to improve P450monooxygenase-catalysis as demonstrated by Griengl and coworkers. [190][191][192][193] For example Beauveria bassiana cannot convert cyclopentanone whereas the corresponding N-benzoylspirooxazolidine was converted smoothly by the same organism (Scheme 13).…”