Expanding the Scope of Arylsulfonylacetylenes as Alkynylating Reagents and Mechanistic Insights in the Formation of Csp2?Csp and Csp3?Csp Bonds from Organolithiums |
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Authors: | Prof Dr José Luis García Ruano Dr José Alemán Leyre Marzo Dr Cuauhtémoc Alvarado Dr Mariola Tortosa Dr Sergio Díaz‐Tendero Dr Alberto Fraile |
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Institution: | 1. Departamento de Química Orgánica (Módulo 1), Universidad Autónoma de Madrid, Fax: (+) 3491497466;2. Departamento de Química (Módulo 13), Universidad Autónoma de Madrid, Cantoblanco, 28049‐Madrid (Spain) |
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Abstract: | We describe the unexpected behavior of the arylsulfonylacetylenes, which suffer an “anti‐Michael” addition of organolithiums producing their alkynylation under very mild conditions. The broad scope, excellent yields, and simplicity of the experimental procedure are the main features of this methodology. A rational explanation of all these results can be achieved by theoretical calculations, which suggest that the association of the organolithiums to the electrophile is a previous step of their intramolecular attack and is responsible for the unexpected “anti‐Michael” reactions observed for substituted sulfonylacetylenes. |
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Keywords: | alkynylation anti‐Michael reactions density functional calculations organolithiums sulfonylacetylenes |
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