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Asymmetric Enzymatic Synthesis of Allylic Amines: A Sigmatropic Rearrangement Strategy

Prier, Christopher K. and Hyster, Todd K. and Farwell, Christopher C. and Huang, Audrey and Arnold, Frances H. (2016) Asymmetric Enzymatic Synthesis of Allylic Amines: A Sigmatropic Rearrangement Strategy. Angewandte Chemie International Edition, 55 (15). pp. 4711-4715. ISSN 1433-7851. PMCID PMC4818679. doi:10.1002/anie.201601056.

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Sigmatropic rearrangements, while rare in biology, offer opportunities for the efficient and selective synthesis of complex chemical motifs. A “P411” serine-ligated variant of cytochrome P450_(BM3) has been engineered to initiate a sulfimidation/[2,3]-sigmatropic rearrangement sequence in whole E. coli cells, a non-natural function for any enzyme, providing access to enantioenriched, protected allylic amines. Five mutations in the enzyme substantially enhance its activity toward this new function, demonstrating the evolvability of the catalyst toward challenging nitrene transfer reactions. The evolved catalyst additionally performs the highly enantioselective imidation of non-allylic sulfides.

Item Type:Article
Related URLs:
URLURL TypeDescription CentralArticle
Prier, Christopher K.0000-0003-0902-1636
Hyster, Todd K.0000-0003-3560-355X
Arnold, Frances H.0000-0002-4027-364X
Alternate Title:Asymmetric Enzymatic Synthesis of Allylic Amines:A Sigmatropic Rearrangement Strategy
Additional Information:© 2016 Wiley-VCH Verlag GmbH & Co. Received: February 1, 2016. First published: 11 March 2016. Our research is supported by the National Science Foundation, Division of Molecular and Cellular Biosciences (grant MCB-1513007). C.K.P. thanks the Resnick Sustainability Institute for a postdoctoral fellowship. T.H.K. and C.C.F. were supported by a Ruth L. Kirschstein National Research Service Award (F32GM108143) and an NSF Graduate Research Fellowship, respectively. We thank Dr. Scott Virgil and the Center for Catalysis and Chemical Synthesis at Caltech for assistance with chiral chromatography.
Group:Resnick Sustainability Institute
Funding AgencyGrant Number
Ruth L. Kirschstein National Research Service AwardsF32GM108143
Resnick Sustainability InstituteUNSPECIFIED
NSF Graduate Research FellowshipUNSPECIFIED
Subject Keywords:amination · biocatalysis · cytochrome P450 · directed evolution · nitrene transfer
Issue or Number:15
PubMed Central ID:PMC4818679
Record Number:CaltechAUTHORS:20160317-072334231
Persistent URL:
Official Citation:C. K. Prier, T. K. Hyster, C. C. Farwell, A. Huang, F. H. Arnold, Angew. Chem. Int. Ed. 2016, 55, 4711.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:65407
Deposited By: Ruth Sustaita
Deposited On:17 Mar 2016 20:08
Last Modified:05 May 2022 18:26

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