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Synfacts 2022; 18(06): 0627
DOI: 10.1055/s-0041-1737470
Metals in Synthesis

Biocatalytic Enantioselective 1-Carbon Ring Expansion via 1,2-Stevens Rearrangement

Contributor(s):
Mark Lautens
,
Austin D. Marchese
Miller DC, Lal RG, Marchetti LA, Arnold FH. * California Institute of Technology, Pasadena, USA
Biocatalytic One-Carbon Ring Expansion of Aziridines to Azetidines via a Highly Enantioselective [1,2]-Stevens Rearrangement.

J. Am. Chem. Soc. 2022;
144: 4739-4745
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Key words

biocatalysis - iron catalysis - Stevens rearrangement - azetidines

Significance

The Arnold group reports an enantioselective biocatalytic one-carbon ring expansion of acylated aziridines to azetidines via a 1,2-Stevens rearrangement. The reaction was developed starting from hemoproteins, which have previously been demonstrated to enable the transfer of carbenoids in related reactions.


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Comment

Directed evolution using iterative site-saturation mutagenesis (SSM) identified the azetidine synthase, P411-AzetS, as the optimal enzyme. The authors indicate that the solvent-caging effects of the active site influence enantioinduction and reactivity in this process, as free hemin is unsuccessful in catalyzing this reaction.


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Publication History

Article published online:
17 May 2022

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