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Preparative semiconductor photoredox catalysis : an emerging theme in organic synthesis

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Date
09/09/2015
Author
Manley, David W.
Walton, John C.
Funder
EPSRC
Grant ID
EP/I003479/1
Keywords
Carboxylic acids
Free radicals
Organic synthesis
Photocatalysis
Titania
Electron-deficient alkenes
Illuminated titanium-dioxide
Visible-light photocatalysis
Phenyl vinyl ether
Carboxylic-acids
Tertiary-amines
Surface photochemistry
Carbon-Dioxide
Kolbe reaction
Heterogeneous photocatalysis
QD Chemistry
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Abstract
Heterogeneous semiconductor photoredox catalysis (SCPC), particularly with TiO2, is evolving to provide radically new synthetic applications. In this review we describe how photoactivated SCPCs can either (i) interact with a precursor that donates an electron to the semiconductor thus generating a radical cation; or (ii) interact with an acceptor precursor that picks up an electron with production of a radical anion. The radical cations of appropriate donors convert to neutral radicals usually by loss of a proton. The most efficient donors for synthetic purposes contain adjacent functional groups such that the neutral radicals are resonance stabilized. Thus, ET from allylic alkenes and enol ethers generated allyl type radicals that reacted with 1,2-diazine or imine co-reactants to yield functionalized hydrazones or benzylanilines. SCPC with tertiary amines enabled electron-deficient alkenes to be alkylated and furoquinolinones to be accessed. Primary amines on their own led to self-reactions involving C–N coupling and, with terminal diamines, cyclic amines were produced. Carboxylic acids were particularly fruitful affording C-centered radicals that alkylated alkenes and took part in tandem addition cyclizations producing chromenopyrroles; decarboxylative homo-dimerizations were also observed. Acceptors initially yielding radical anions included nitroaromatics and aromatic iodides. The latter led to hydrodehalogenations and cyclizations with suitable precursors. Reductive SCPC also enabled electron-deficient alkenes and aromatic aldehydes to be hydrogenated without the need for hydrogen gas.
Citation
Manley , D W & Walton , J C 2015 , ' Preparative semiconductor photoredox catalysis : an emerging theme in organic synthesis ' , Beilstein Journal of Organic Chemistry , vol. 11 , pp. 1570-1582 . https://doi.org/10.3762/bjoc.11.173
Publication
Beilstein Journal of Organic Chemistry
Status
Peer reviewed
DOI
https://doi.org/10.3762/bjoc.11.173
ISSN
1860-5397
Type
Journal item
Rights
© 2015 Manley and Walton; licensee Beilstein-Institut. This is an Open Access article under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Description
Financial support from EPSRC (Grant EP/I003479/1) and EaStCHEM is gratefully acknowledged.
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  • University of St Andrews Research
URI
http://hdl.handle.net/10023/7570

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