New insights into cyclobutenone rearrangements: A total synthesis of the natural ROS-generating anti-cancer agent cribrostatin 6

Mubina Mohamed; Théo P. Gonçalves; Richard J. Whitby; Helen F. Sneddon; David C. Harrowven

doi:10.1002/chem.201102263

New insights into cyclobutenone rearrangements: A total synthesis of the natural ROS-generating anti-cancer agent cribrostatin 6

Mubina Mohamed, Théo P. Gonçalves, Richard J. Whitby, Helen F. Sneddon, David C. Harrowven^*

^*Corresponding author for this work

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

34 Scopus citations

Abstract

Aryl- and heteroarylcyclobutenone rearrangements proceed in excellent yield under continuous-flow conditions. The former shows a Hammett correlation with σ_I providing strong evidence that electrocyclisation is the rate-determining step and has a late transition state. The reaction has been modelled by using DFT and CCSD(T) methods, with the latter giving excellent correlation with the experimental rate constant. A short and efficient total synthesis of cribrostatin 6, an anti-neoplastic and anti-microbial agent, provides a topical demonstration of the value of this method.

Original language	English (US)
Pages (from-to)	13698-13705
Number of pages	8
Journal	Chemistry - A European Journal
Volume	17
Issue number	49
DOIs	https://doi.org/10.1002/chem.201102263
State	Published - Dec 2 2011

Keywords

density functional calculations
flow chemistry
Hammett correlation
reaction mechanisms
thermochemistry

ASJC Scopus subject areas

Catalysis
Organic Chemistry

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/chem.201102263

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abstract = "Aryl- and heteroarylcyclobutenone rearrangements proceed in excellent yield under continuous-flow conditions. The former shows a Hammett correlation with σI providing strong evidence that electrocyclisation is the rate-determining step and has a late transition state. The reaction has been modelled by using DFT and CCSD(T) methods, with the latter giving excellent correlation with the experimental rate constant. A short and efficient total synthesis of cribrostatin 6, an anti-neoplastic and anti-microbial agent, provides a topical demonstration of the value of this method.",

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T2 - A total synthesis of the natural ROS-generating anti-cancer agent cribrostatin 6

AU - Mohamed, Mubina

AU - Gonçalves, Théo P.

AU - Whitby, Richard J.

AU - Sneddon, Helen F.

AU - Harrowven, David C.

PY - 2011/12/2

Y1 - 2011/12/2

N2 - Aryl- and heteroarylcyclobutenone rearrangements proceed in excellent yield under continuous-flow conditions. The former shows a Hammett correlation with σI providing strong evidence that electrocyclisation is the rate-determining step and has a late transition state. The reaction has been modelled by using DFT and CCSD(T) methods, with the latter giving excellent correlation with the experimental rate constant. A short and efficient total synthesis of cribrostatin 6, an anti-neoplastic and anti-microbial agent, provides a topical demonstration of the value of this method.

AB - Aryl- and heteroarylcyclobutenone rearrangements proceed in excellent yield under continuous-flow conditions. The former shows a Hammett correlation with σI providing strong evidence that electrocyclisation is the rate-determining step and has a late transition state. The reaction has been modelled by using DFT and CCSD(T) methods, with the latter giving excellent correlation with the experimental rate constant. A short and efficient total synthesis of cribrostatin 6, an anti-neoplastic and anti-microbial agent, provides a topical demonstration of the value of this method.

KW - density functional calculations

KW - flow chemistry

KW - Hammett correlation

KW - reaction mechanisms

KW - thermochemistry

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M3 - Article

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AN - SCOPUS:82455219453

SN - 0947-6539

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JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 49

ER -

New insights into cyclobutenone rearrangements: A total synthesis of the natural ROS-generating anti-cancer agent cribrostatin 6

Abstract

Keywords

ASJC Scopus subject areas

UN SDGs

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