St Andrews Research Repository

St Andrews University Home
View Item 
  •   St Andrews Research Repository
  • University of St Andrews Research
  • University of St Andrews Research
  • University of St Andrews Research
  • View Item
  •   St Andrews Research Repository
  • University of St Andrews Research
  • University of St Andrews Research
  • University of St Andrews Research
  • View Item
  •   St Andrews Research Repository
  • University of St Andrews Research
  • University of St Andrews Research
  • University of St Andrews Research
  • View Item
  • Login
JavaScript is disabled for your browser. Some features of this site may not work without it.

Catalytic enantioselective synthesis of α-chiral azaheteroaryl ethylamines by asymmetric protonation

Thumbnail
View/Open
ACIE_201806956_AAM.pdf (1.553Mb)
Date
01/08/2018
Author
Xu, Chao
Muir, Calum
Leach, Andrew
Kennedy, Alan
Watson, Allan J. B.
Funder
The Leverhulme Trust
Grant ID
RPG-2015-308
Keywords
Asymmetric catalysis
Brønsted acid
DFT
Heterocycles
Stereochemistry
QD Chemistry
DAS
Metadata
Show full item record
Altmetrics Handle Statistics
Altmetrics DOI Statistics
Abstract
The direct enantioselective synthesis of chiral azaheteroaryl ethylamines from vinyl‐substituted N‐heterocycles and anilines is reported. A chiral phosphoric acid (CPA) catalyst promotes dearomatizing aza‐Michael addition to give a prochiral exocyclic aryl enamine, which undergoes asymmetric protonation upon rearomatization. The reaction accommodates a broad range of N‐heterocycles, nucleophiles, and substituents on the prochiral centre, generating the products in high enantioselectivity. DFT studies support a facile nucleophilic addition based on catalyst‐induced LUMO lowering, with site‐selective, rate‐limiting, intramolecular asymmetric proton transfer from the ion‐paired prochiral intermediate.
Citation
Xu , C , Muir , C , Leach , A , Kennedy , A & Watson , A J B 2018 , ' Catalytic enantioselective synthesis of α-chiral azaheteroaryl ethylamines by asymmetric protonation ' , Angewandte Chemie International Edition , vol. In press . https://doi.org/10.1002/anie.201806956
Publication
Angewandte Chemie International Edition
Status
Peer reviewed
DOI
https://doi.org/10.1002/anie.201806956
ISSN
1433-7851
Type
Journal article
Rights
© 2018 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim. This work has been made available online in accordance with the publisher’s policies. This is the author created accepted version manuscript following peer review and as such may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1002/anie.201806956
Description
The authors thank the Leverhulme Trust for funding (C.X.; RPG-2015- 308) and GSK for a PhD studentship (C.W.M.). The authors thank the EPSRC UK National Mass Spectrometry Facility at Swansea University for analyses.
Collections
  • University of St Andrews Research
URI
http://hdl.handle.net/10023/18223

Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.

Advanced Search

Browse

All of RepositoryCommunities & CollectionsBy Issue DateNamesTitlesSubjectsClassificationTypeFunderThis CollectionBy Issue DateNamesTitlesSubjectsClassificationTypeFunder

My Account

Login

Open Access

To find out how you can benefit from open access to research, see our library web pages and Open Access blog. For open access help contact: openaccess@st-andrews.ac.uk.

Accessibility

Read our Accessibility statement.

How to submit research papers

The full text of research papers can be submitted to the repository via Pure, the University's research information system. For help see our guide: How to deposit in Pure.

Electronic thesis deposit

Help with deposit.

Repository help

For repository help contact: Digital-Repository@st-andrews.ac.uk.

Give Feedback

Cookie policy

This site may use cookies. Please see Terms and Conditions.

Usage statistics

COUNTER-compliant statistics on downloads from the repository are available from the IRUS-UK Service. Contact us for information.

© University of St Andrews Library

University of St Andrews is a charity registered in Scotland, No SC013532.

  • Facebook
  • Twitter