Biocatalytic Aromaticity-Breaking Epoxidation of Naphthalene

Gideon James Grogan; Adrian C. Whitwood; Wuyuan Zhang; Huanhuan Li; Sabry Younes; Patricia Gomez de Santos; Florian Tieves; Martin Pabst; Miguel Alcalde; Frank Hollmann

doi:10.1021/acscatal.0c05588

Biocatalytic Aromaticity-Breaking Epoxidation of Naphthalene

Gideon James Grogan, Adrian C. Whitwood, Wuyuan Zhang, Huanhuan Li, Sabry Younes, Patricia Gomez de Santos, Florian Tieves, Martin Pabst, Miguel Alcalde, Frank Hollmann

Chemistry

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

Abstract

Aromatic hydroxylation reactions catalyzed by heme-thiolate enzymes proceed via an epoxide intermediate.
These aromatic epoxides could be valuable building blocks for organic synthesis giving access to a range of chiral transdisubstituted
cyclohexadiene synthons. Here we show that naphthalene epoxides generated by fungal peroxygenases can
be subjected to nucleophilic ring opening yielding non-racemic trans-disubstituted cyclohexadiene derivates, which in turn
can be used for further chemical transformations. Following the ring-opening reactions, the synthetic possibility of
cyclohexadiene derivates also demonstrated by four examples yielding functional compounds. This novel approach may
represent a promising shortcut for the synthesis of natural products and APIs.

Original language	English
Pages (from-to)	2644-2649
Number of pages	6
Journal	ACS Catalysis
Volume	11
Early online date	12 Feb 2021
DOIs	https://doi.org/10.1021/acscatal.0c05588
Publication status	E-pub ahead of print - 12 Feb 2021

Bibliographical note

Access to Document

10.1021/acscatal.0c05588Licence: CC BY

acscatal.0c05588
© 2021 The Authors. Published by American Chemical Society
Final published version, 2.68 MBLicence: CC BY

Cite this

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title = "Biocatalytic Aromaticity-Breaking Epoxidation of Naphthalene",

abstract = "Aromatic hydroxylation reactions catalyzed by heme-thiolate enzymes proceed via an epoxide intermediate.These aromatic epoxides could be valuable building blocks for organic synthesis giving access to a range of chiral transdisubstitutedcyclohexadiene synthons. Here we show that naphthalene epoxides generated by fungal peroxygenases canbe subjected to nucleophilic ring opening yielding non-racemic trans-disubstituted cyclohexadiene derivates, which in turncan be used for further chemical transformations. Following the ring-opening reactions, the synthetic possibility ofcyclohexadiene derivates also demonstrated by four examples yielding functional compounds. This novel approach mayrepresent a promising shortcut for the synthesis of natural products and APIs.",

author = "Grogan, {Gideon James} and Whitwood, {Adrian C.} and Wuyuan Zhang and Huanhuan Li and Sabry Younes and {Gomez de Santos}, Patricia and Florian Tieves and Martin Pabst and Miguel Alcalde and Frank Hollmann",

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doi = "10.1021/acscatal.0c05588",

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AU - Grogan, Gideon James

AU - Whitwood, Adrian C.

AU - Zhang, Wuyuan

AU - Li, Huanhuan

AU - Younes, Sabry

AU - Gomez de Santos, Patricia

AU - Tieves, Florian

AU - Pabst, Martin

AU - Alcalde, Miguel

AU - Hollmann, Frank

PY - 2021/2/12

Y1 - 2021/2/12

N2 - Aromatic hydroxylation reactions catalyzed by heme-thiolate enzymes proceed via an epoxide intermediate.These aromatic epoxides could be valuable building blocks for organic synthesis giving access to a range of chiral transdisubstitutedcyclohexadiene synthons. Here we show that naphthalene epoxides generated by fungal peroxygenases canbe subjected to nucleophilic ring opening yielding non-racemic trans-disubstituted cyclohexadiene derivates, which in turncan be used for further chemical transformations. Following the ring-opening reactions, the synthetic possibility ofcyclohexadiene derivates also demonstrated by four examples yielding functional compounds. This novel approach mayrepresent a promising shortcut for the synthesis of natural products and APIs.

AB - Aromatic hydroxylation reactions catalyzed by heme-thiolate enzymes proceed via an epoxide intermediate.These aromatic epoxides could be valuable building blocks for organic synthesis giving access to a range of chiral transdisubstitutedcyclohexadiene synthons. Here we show that naphthalene epoxides generated by fungal peroxygenases canbe subjected to nucleophilic ring opening yielding non-racemic trans-disubstituted cyclohexadiene derivates, which in turncan be used for further chemical transformations. Following the ring-opening reactions, the synthetic possibility ofcyclohexadiene derivates also demonstrated by four examples yielding functional compounds. This novel approach mayrepresent a promising shortcut for the synthesis of natural products and APIs.

U2 - 10.1021/acscatal.0c05588

DO - 10.1021/acscatal.0c05588

M3 - Article

SN - 2155-5435

VL - 11

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JO - ACS Catalysis

JF - ACS Catalysis

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