An Alternative to the Classical α-Arylation: The Transfer of an Intact 2-Iodoaryl from ArI(O2CCF3)2†
Dr. Zhiyu Jia
Department of Chemistry and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Autònoma de Barcelona, Bellaterra (Spain)
Search for more papers by this authorDr. Erik Gálvez
Department of Chemistry and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Autònoma de Barcelona, Bellaterra (Spain)
Search for more papers by this authorProf. Dr. Rosa María Sebastián
Department of Chemistry and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Autònoma de Barcelona, Bellaterra (Spain)
Search for more papers by this authorProf. Dr. Roser Pleixats
Department of Chemistry and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Autònoma de Barcelona, Bellaterra (Spain)
Search for more papers by this authorDr. Ángel Álvarez-Larena
Servei de Difracció de Raigs X, Universitat Autònoma de Barcelona
Search for more papers by this authorDr. Eddy Martin
Institute of Chemical Research of Catalonia (ICIQ), Avda. Països Catalans 16, 43007 Tarragona (Spain)
Search for more papers by this authorCorresponding Author
Prof. Dr. Adelina Vallribera
Department of Chemistry and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Autònoma de Barcelona, Bellaterra (Spain)
Adelina Vallribera, Department of Chemistry and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Autònoma de Barcelona, Bellaterra (Spain)
Alexandr Shafir, Institute of Chemical Research of Catalonia (ICIQ), Avda. Països Catalans 16, 43007 Tarragona (Spain)
Search for more papers by this authorCorresponding Author
Dr. Alexandr Shafir
Institute of Chemical Research of Catalonia (ICIQ), Avda. Països Catalans 16, 43007 Tarragona (Spain)
Adelina Vallribera, Department of Chemistry and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Autònoma de Barcelona, Bellaterra (Spain)
Alexandr Shafir, Institute of Chemical Research of Catalonia (ICIQ), Avda. Països Catalans 16, 43007 Tarragona (Spain)
Search for more papers by this authorDr. Zhiyu Jia
Department of Chemistry and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Autònoma de Barcelona, Bellaterra (Spain)
Search for more papers by this authorDr. Erik Gálvez
Department of Chemistry and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Autònoma de Barcelona, Bellaterra (Spain)
Search for more papers by this authorProf. Dr. Rosa María Sebastián
Department of Chemistry and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Autònoma de Barcelona, Bellaterra (Spain)
Search for more papers by this authorProf. Dr. Roser Pleixats
Department of Chemistry and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Autònoma de Barcelona, Bellaterra (Spain)
Search for more papers by this authorDr. Ángel Álvarez-Larena
Servei de Difracció de Raigs X, Universitat Autònoma de Barcelona
Search for more papers by this authorDr. Eddy Martin
Institute of Chemical Research of Catalonia (ICIQ), Avda. Països Catalans 16, 43007 Tarragona (Spain)
Search for more papers by this authorCorresponding Author
Prof. Dr. Adelina Vallribera
Department of Chemistry and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Autònoma de Barcelona, Bellaterra (Spain)
Adelina Vallribera, Department of Chemistry and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Autònoma de Barcelona, Bellaterra (Spain)
Alexandr Shafir, Institute of Chemical Research of Catalonia (ICIQ), Avda. Països Catalans 16, 43007 Tarragona (Spain)
Search for more papers by this authorCorresponding Author
Dr. Alexandr Shafir
Institute of Chemical Research of Catalonia (ICIQ), Avda. Països Catalans 16, 43007 Tarragona (Spain)
Adelina Vallribera, Department of Chemistry and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Autònoma de Barcelona, Bellaterra (Spain)
Alexandr Shafir, Institute of Chemical Research of Catalonia (ICIQ), Avda. Països Catalans 16, 43007 Tarragona (Spain)
Search for more papers by this authorThis work was supported by the ICIQ, MICINN (CTQ2011-22649), the MEC (Cons. Ing. CSD2007-00006), the Generalitat de Catalunya (2014SGR1192 and 2014SGR1105), and the China Scholarship Council (fellowship to Z.J.). We thank MINECO for support through grant CTQ2013-46705-R and Severo Ochoa Excellence Accreditation 2014–2018 (SEV-2013-0319).
Abstract
The α-arylation of carbonyl compounds is generally accomplished under basic conditions, both under metal catalysis and via aryl transfer from the diaryl λ3-iodanes. Here, we describe an alternative metal-free α-arylation using ArI(O2CCF3)2 as the source of a 2-iodoaryl group. The reaction is applicable to activated ketones, such as α-cyanoketones, and works with substituted aryliodanes. This formal CH functionalization reaction is thought to proceed through a [3,3] rearrangement of an iodonium enolate. The final α-(2-iodoaryl)ketones are versatile synthetic building blocks.
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