Oxidative radical cyclizations of diketopiperazines bearing an amidomalonate unit. Heterointermediate reaction sequences toward the asperparalines and stephacidins

Tynchtyk Amatov; Martin Gebauer; Radek Pohl; Ivana Cisařová; Ullrich Jahn

doi:10.1080/10715762.2016.1223295

Oxidative radical cyclizations of diketopiperazines bearing an amidomalonate unit. Heterointermediate reaction sequences toward the asperparalines and stephacidins

Tynchtyk Amatov, Martin Gebauer, Radek Pohl, Ivana Cisařová, Ullrich Jahn

Chemistry

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

Abstract

A novel approach to the diazabicyclo[2.2.2]octane core of prenylated bridged diketopiperazine alkaloids is described by direct oxidative cyclizations of functionalized diketopiperazines mediated by ferrocenium hexafluorophosphate or the Mn(OAc)₃•2H₂O/Cu(OTf)₂ system. Divergent reaction pathways take place depending on the substitution pattern of the substrates and the oxidation conditions such as temperature or the presence or absence of persistent radical TEMPO. For ester-substituted diketopiperazines, the ester group exerts a significant influence on the reaction outcome and stereochemistry of the radical cyclizations.

Original language	English (US)
Pages (from-to)	S6-S17
Journal	Free Radical Research
Volume	50
DOIs	https://doi.org/10.1080/10715762.2016.1223295
State	Published - Nov 1 2016

Keywords

Alkaloids
diketopiperazines
oxidation
radical cyclizations
single electron transfer

ASJC Scopus subject areas

Biochemistry

Access to Document

10.1080/10715762.2016.1223295

Cite this

@article{fb4e97948fde40abb1b16e603cbb780a,

title = "Oxidative radical cyclizations of diketopiperazines bearing an amidomalonate unit. Heterointermediate reaction sequences toward the asperparalines and stephacidins",

abstract = "A novel approach to the diazabicyclo[2.2.2]octane core of prenylated bridged diketopiperazine alkaloids is described by direct oxidative cyclizations of functionalized diketopiperazines mediated by ferrocenium hexafluorophosphate or the Mn(OAc)3•2H2O/Cu(OTf)2 system. Divergent reaction pathways take place depending on the substitution pattern of the substrates and the oxidation conditions such as temperature or the presence or absence of persistent radical TEMPO. For ester-substituted diketopiperazines, the ester group exerts a significant influence on the reaction outcome and stereochemistry of the radical cyclizations.",

keywords = "Alkaloids, diketopiperazines, oxidation, radical cyclizations, single electron transfer",

author = "Tynchtyk Amatov and Martin Gebauer and Radek Pohl and Ivana Cisa{\v r}ov{\'a} and Ullrich Jahn",

note = "Publisher Copyright: {\textcopyright} 2016 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group.",

year = "2016",

month = nov,

day = "1",

doi = "10.1080/10715762.2016.1223295",

language = "English (US)",

volume = "50",

pages = "S6--S17",

journal = "Free Radical Research",

issn = "1071-5762",

publisher = "Informa Healthcare",

}

TY - JOUR

T1 - Oxidative radical cyclizations of diketopiperazines bearing an amidomalonate unit. Heterointermediate reaction sequences toward the asperparalines and stephacidins

AU - Amatov, Tynchtyk

AU - Gebauer, Martin

AU - Pohl, Radek

AU - Cisařová, Ivana

AU - Jahn, Ullrich

PY - 2016/11/1

Y1 - 2016/11/1

N2 - A novel approach to the diazabicyclo[2.2.2]octane core of prenylated bridged diketopiperazine alkaloids is described by direct oxidative cyclizations of functionalized diketopiperazines mediated by ferrocenium hexafluorophosphate or the Mn(OAc)3•2H2O/Cu(OTf)2 system. Divergent reaction pathways take place depending on the substitution pattern of the substrates and the oxidation conditions such as temperature or the presence or absence of persistent radical TEMPO. For ester-substituted diketopiperazines, the ester group exerts a significant influence on the reaction outcome and stereochemistry of the radical cyclizations.

AB - A novel approach to the diazabicyclo[2.2.2]octane core of prenylated bridged diketopiperazine alkaloids is described by direct oxidative cyclizations of functionalized diketopiperazines mediated by ferrocenium hexafluorophosphate or the Mn(OAc)3•2H2O/Cu(OTf)2 system. Divergent reaction pathways take place depending on the substitution pattern of the substrates and the oxidation conditions such as temperature or the presence or absence of persistent radical TEMPO. For ester-substituted diketopiperazines, the ester group exerts a significant influence on the reaction outcome and stereochemistry of the radical cyclizations.

KW - Alkaloids

KW - diketopiperazines

KW - oxidation

KW - radical cyclizations

KW - single electron transfer

UR - http://www.scopus.com/inward/record.url?scp=84994107369&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84994107369&partnerID=8YFLogxK

U2 - 10.1080/10715762.2016.1223295

DO - 10.1080/10715762.2016.1223295

M3 - Article

C2 - 27806645

AN - SCOPUS:84994107369

SN - 1071-5762

VL - 50

SP - S6-S17

JO - Free Radical Research

JF - Free Radical Research

ER -

Oxidative radical cyclizations of diketopiperazines bearing an amidomalonate unit. Heterointermediate reaction sequences toward the asperparalines and stephacidins

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this