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Shedding light on the use of Cu(II)-salen complexes in the A3 coupling reaction

Shedding light on the use of Cu(II)-salen complexes in the A3 coupling reaction
Shedding light on the use of Cu(II)-salen complexes in the A3 coupling reaction
One Cu(II) complex, {Cu(II)L} (1S), has been synthesised, in two high yielding steps under ambient conditions, and characterised by single-crystal X-Ray diffraction (SXRD), IR, UV-Vis, circular dichroism (CD), elemental analysis, thermogravimetric analysis (TGA) and electron spray ionization mass spectroscopy (ESI-MS). This air-stable compound enables the generation, at room temperature and in open-air, of twenty propargylamines, nine new, from secondary amines, aliphatic aldehydes and alkynes with a broad scope with yields up to 99%. Catalyst loadings can be as low as 1 mol%, while the recovered material retains its structural integrity and can be used up to 5 times without loss of its activity. Control experiments, SXRD, cyclic voltammetry and theoretical studies shed light on the mechanism revealing that the key to success is the use of phenoxido salen based ligands. These ligands orchestrate topological control permitting alkyne binding with concomitant activation of the C–H bond and simultaneously acting as a template temporarily accommodating the abstracted acetylenic proton, and continuously generating, via in situ formed radicals and a Single Electron Transfer (SET) mechanism, a transient Cu(I) active site to facilitate this transformation. The scope and limitations of this protocol are discussed and presented.
0300-9246
Sampani, Stavroula I.
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Zdorichenko, Victor
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Danopoulou, Marianna
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Leech, Matthew C.
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Lam, Kevin
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Abdul-Sada, Alaa
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Tizzard, Graham J.
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Coles, Simon J.
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Tsipis, Athanassios C.
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Kostakis, George E.
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Sampani, Stavroula I.
346af07d-2a76-47b8-b21d-7416ebb69efc
Zdorichenko, Victor
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Danopoulou, Marianna
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Leech, Matthew C.
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Lam, Kevin
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Abdul-Sada, Alaa
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Tizzard, Graham J.
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Coles, Simon J.
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Tsipis, Athanassios C.
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Kostakis, George E.
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Sampani, Stavroula I., Zdorichenko, Victor, Danopoulou, Marianna, Leech, Matthew C., Lam, Kevin, Abdul-Sada, Alaa, Tizzard, Graham J., Coles, Simon J., Tsipis, Athanassios C. and Kostakis, George E. (2019) Shedding light on the use of Cu(II)-salen complexes in the A3 coupling reaction. Dalton Transactions. (doi:10.1039/C9DT04146J).

Record type: Article

Abstract

One Cu(II) complex, {Cu(II)L} (1S), has been synthesised, in two high yielding steps under ambient conditions, and characterised by single-crystal X-Ray diffraction (SXRD), IR, UV-Vis, circular dichroism (CD), elemental analysis, thermogravimetric analysis (TGA) and electron spray ionization mass spectroscopy (ESI-MS). This air-stable compound enables the generation, at room temperature and in open-air, of twenty propargylamines, nine new, from secondary amines, aliphatic aldehydes and alkynes with a broad scope with yields up to 99%. Catalyst loadings can be as low as 1 mol%, while the recovered material retains its structural integrity and can be used up to 5 times without loss of its activity. Control experiments, SXRD, cyclic voltammetry and theoretical studies shed light on the mechanism revealing that the key to success is the use of phenoxido salen based ligands. These ligands orchestrate topological control permitting alkyne binding with concomitant activation of the C–H bond and simultaneously acting as a template temporarily accommodating the abstracted acetylenic proton, and continuously generating, via in situ formed radicals and a Single Electron Transfer (SET) mechanism, a transient Cu(I) active site to facilitate this transformation. The scope and limitations of this protocol are discussed and presented.

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Accepted/In Press date: 14 November 2019
e-pub ahead of print date: 15 November 2019

Identifiers

Local EPrints ID: 436193
URI: http://eprints.soton.ac.uk/id/eprint/436193
ISSN: 0300-9246
PURE UUID: cbd9ae40-5c38-4c48-b7e6-9314ec896388
ORCID for Graham J. Tizzard: ORCID iD orcid.org/0000-0002-1577-5779
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 03 Dec 2019 17:30
Last modified: 26 Nov 2021 05:16

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Contributors

Author: Stavroula I. Sampani
Author: Victor Zdorichenko
Author: Marianna Danopoulou
Author: Matthew C. Leech
Author: Kevin Lam
Author: Alaa Abdul-Sada
Author: Simon J. Coles ORCID iD
Author: Athanassios C. Tsipis
Author: George E. Kostakis

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