Full Paper
An Investigation into the Stephens–Castro Synthesis of Dehydrotriaryl[12]annulenes: Factors Influencing the Cyclotrimerization
Paul N. W. Baxter,
Abdelaziz Al Ouahabi,
Lydia Karmazin,
Alexandre Varnek,
Jean-Marc Strub,
Sarah Cianferani,
Corresponding Author
Paul N. W. Baxter
Institut Charles Sadron, UPR 22 (CNRS-UdS), 23 rue du Loess, 67034 Strasbourg, France
Institut Charles Sadron, UPR 22 (CNRS-UdS), 23 rue du Loess, 67034 Strasbourg, France
E-mail: [email protected]
Search for more papers by this authorAbdelaziz Al Ouahabi
Institut Charles Sadron, UPR 22 (CNRS-UdS), 23 rue du Loess, 67034 Strasbourg, France
Search for more papers by this authorLydia Karmazin
Service de Radiocristallographie, Fédération de Chimie “Le Bel” FR2010, Tour de Chimie, 1 rue Blaise Pascal, 67008 Strasbourg, France
Search for more papers by this authorAlexandre Varnek
Laboratoire de Chémoinformatique, UMR 7140 CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67000 Strasbourg, France
Search for more papers by this authorJean-Marc Strub
Laboratoire de Spectrométrie de Masse Bio-Organique, Département des Sciences Analytiques IPHC, UMR 7178 (CNRS-UdS) ECPM, 25 rue Becquerel, 67087 Strasbourg, France
Search for more papers by this authorSarah Cianferani
Laboratoire de Spectrométrie de Masse Bio-Organique, Département des Sciences Analytiques IPHC, UMR 7178 (CNRS-UdS) ECPM, 25 rue Becquerel, 67087 Strasbourg, France
Search for more papers by this authorPaul N. W. Baxter,
Abdelaziz Al Ouahabi,
Lydia Karmazin,
Alexandre Varnek,
Jean-Marc Strub,
Sarah Cianferani,
Corresponding Author
Paul N. W. Baxter
Institut Charles Sadron, UPR 22 (CNRS-UdS), 23 rue du Loess, 67034 Strasbourg, France
Institut Charles Sadron, UPR 22 (CNRS-UdS), 23 rue du Loess, 67034 Strasbourg, France
E-mail: [email protected]
Search for more papers by this authorAbdelaziz Al Ouahabi
Institut Charles Sadron, UPR 22 (CNRS-UdS), 23 rue du Loess, 67034 Strasbourg, France
Search for more papers by this authorLydia Karmazin
Service de Radiocristallographie, Fédération de Chimie “Le Bel” FR2010, Tour de Chimie, 1 rue Blaise Pascal, 67008 Strasbourg, France
Search for more papers by this authorAlexandre Varnek
Laboratoire de Chémoinformatique, UMR 7140 CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67000 Strasbourg, France
Search for more papers by this authorJean-Marc Strub
Laboratoire de Spectrométrie de Masse Bio-Organique, Département des Sciences Analytiques IPHC, UMR 7178 (CNRS-UdS) ECPM, 25 rue Becquerel, 67087 Strasbourg, France
Search for more papers by this authorSarah Cianferani
Laboratoire de Spectrométrie de Masse Bio-Organique, Département des Sciences Analytiques IPHC, UMR 7178 (CNRS-UdS) ECPM, 25 rue Becquerel, 67087 Strasbourg, France
Search for more papers by this authorGraphical Abstract
An exploration of the reaction conditions under which the Stephens–Castro reaction of o-iodoarylethynylcuprates 6 and 8 preferentially afford macrocyclic dehydrotriaryl[12]annulenes 1 and 2 rather than giving polymeric products, suggest a mechanism that involves initial assembly of the ethynylcuprates into a soluble oligonuclear structure preorganized for cyclotrimerization.
Abstract
Detailed investigation into the CuX/base/phosphine modified Stephens–Castro syntheses of dehydrotriaryl[12]annulenes 1–3 have shown that cyclization is suppressed by excess CuX, strong donor ligands, high dilution conditions, and thermally unstable ethynylcuprate monomers. Surprisingly, intermediate dimer 16 plays only a minor role in the formation of 2 and 4. Overall, our findings are consistent with a cyclization pathway governed more by the nature of prior self-association of the ethynylcuprate monomers. Crystallographic characterization of tetrameric by-product 4, is also reported and revealed that it assembles into tubular stacks in the solid state.
Supporting Information
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References
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