Regio- and stereodivergent antibiotic oxidative carbocyclizations catalysed by Rieske oxygenase-like enzymes

Paulina K. Sydor; Sarah M. Barry; O. M. Odulate; Francisco Barona- Gomez; Stuart W. Haynes; Christophe Corre; Lijiang Song; Gregory L. Challis

doi:10.1038/nchem.1024

Regio- and stereodivergent antibiotic oxidative carbocyclizations catalysed by Rieske oxygenase-like enzymes

Paulina K. Sydor, Sarah M. Barry, O. M. Odulate, Francisco Barona- Gomez, Stuart W. Haynes, Christophe Corre, Lijiang Song, Gregory L. Challis

Chemistry

University of Warwick

Research output: Contribution to journal › Article › peer-review

104 Citations (Scopus)

Abstract

Oxidative cyclizations, exemplified by the biosynthetic assembly of the penicillin nucleus from a tripeptide precursor, are arguably the most synthetically powerful implementation of C–H activation reactions in nature. Here, we show that Rieske oxygenase-like enzymes mediate regio- and stereodivergent oxidative cyclizations to form 10- and 12-membered carbocyclic rings in the key steps of the biosynthesis of the antibiotics streptorubin B and metacycloprodigiosin, respectively. These reactions represent the first examples of oxidative carbocyclizations catalysed by non-haem iron-dependent oxidases and define a novel type of catalytic activity for Rieske enzymes. A better understanding of how these enzymes achieve such remarkable regio- and stereocontrol in the functionalization of unactivated hydrocarbon chains will greatly facilitate the development of selective man-made C–H activation catalysts.

Original language	English
Article number	N/A
Pages (from-to)	388-392
Number of pages	5
Journal	Nature Chemistry
Volume	3
Issue number	5
DOIs	https://doi.org/10.1038/nchem.1024
Publication status	Published - May 2011

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title = "Regio- and stereodivergent antibiotic oxidative carbocyclizations catalysed by Rieske oxygenase-like enzymes",

abstract = "Oxidative cyclizations, exemplified by the biosynthetic assembly of the penicillin nucleus from a tripeptide precursor, are arguably the most synthetically powerful implementation of C–H activation reactions in nature. Here, we show that Rieske oxygenase-like enzymes mediate regio- and stereodivergent oxidative cyclizations to form 10- and 12-membered carbocyclic rings in the key steps of the biosynthesis of the antibiotics streptorubin B and metacycloprodigiosin, respectively. These reactions represent the first examples of oxidative carbocyclizations catalysed by non-haem iron-dependent oxidases and define a novel type of catalytic activity for Rieske enzymes. A better understanding of how these enzymes achieve such remarkable regio- and stereocontrol in the functionalization of unactivated hydrocarbon chains will greatly facilitate the development of selective man-made C–H activation catalysts.",

author = "Sydor, {Paulina K.} and Barry, {Sarah M.} and Odulate, {O. M.} and {Barona- Gomez}, Francisco and Haynes, {Stuart W.} and Christophe Corre and Lijiang Song and Challis, {Gregory L.}",

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T1 - Regio- and stereodivergent antibiotic oxidative carbocyclizations catalysed by Rieske oxygenase-like enzymes

AU - Sydor, Paulina K.

AU - Barry, Sarah M.

AU - Odulate, O. M.

AU - Barona- Gomez, Francisco

AU - Haynes, Stuart W.

AU - Corre, Christophe

AU - Song, Lijiang

AU - Challis, Gregory L.

PY - 2011/5

Y1 - 2011/5

N2 - Oxidative cyclizations, exemplified by the biosynthetic assembly of the penicillin nucleus from a tripeptide precursor, are arguably the most synthetically powerful implementation of C–H activation reactions in nature. Here, we show that Rieske oxygenase-like enzymes mediate regio- and stereodivergent oxidative cyclizations to form 10- and 12-membered carbocyclic rings in the key steps of the biosynthesis of the antibiotics streptorubin B and metacycloprodigiosin, respectively. These reactions represent the first examples of oxidative carbocyclizations catalysed by non-haem iron-dependent oxidases and define a novel type of catalytic activity for Rieske enzymes. A better understanding of how these enzymes achieve such remarkable regio- and stereocontrol in the functionalization of unactivated hydrocarbon chains will greatly facilitate the development of selective man-made C–H activation catalysts.

AB - Oxidative cyclizations, exemplified by the biosynthetic assembly of the penicillin nucleus from a tripeptide precursor, are arguably the most synthetically powerful implementation of C–H activation reactions in nature. Here, we show that Rieske oxygenase-like enzymes mediate regio- and stereodivergent oxidative cyclizations to form 10- and 12-membered carbocyclic rings in the key steps of the biosynthesis of the antibiotics streptorubin B and metacycloprodigiosin, respectively. These reactions represent the first examples of oxidative carbocyclizations catalysed by non-haem iron-dependent oxidases and define a novel type of catalytic activity for Rieske enzymes. A better understanding of how these enzymes achieve such remarkable regio- and stereocontrol in the functionalization of unactivated hydrocarbon chains will greatly facilitate the development of selective man-made C–H activation catalysts.

U2 - 10.1038/nchem.1024

DO - 10.1038/nchem.1024

M3 - Article

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JO - Nature Chemistry

JF - Nature Chemistry

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ER -

Regio- and stereodivergent antibiotic oxidative carbocyclizations catalysed by Rieske oxygenase-like enzymes

Abstract

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