Cu-Catalyzed Silylation of Alkynes: A Traceless 2-Pyridylsulfonyl Controller Allows Access to Either Regioisomer on Demand
| Autor: | Pablo Mauleón, Alfonso Garcia‐Rubia, Jose A. Romero‐Revilla, Juan C. Carretero, Ramón Gómez Arrayás |
|---|---|
| Přispěvatelé: | UAM. Departamento de Química Orgánica |
| Rok vydání: | 2015 |
| Předmět: |
chemistry.chemical_classification
Sulfonyl Allylic rearrangement Silylation Chemistry Hydrosilylation Allene Alkyne Química General Chemistry Biochemistry Catalysis Silylcupration Vinyl silane chemistry.chemical_compound 2-pyridyl sulfone Colloid and Surface Chemistry Cu-catalysis Organic chemistry Chemoselectivity |
| Zdroj: | Biblos-e Archivo. Repositorio Institucional de la UAM instname |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/jacs.5b02667 |
| Popis: | This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/jacs.5b02667 The Cu-catalyzed silylation of terminal and internal alkynes bearing a 2-pyridyl sulfonyl group (SO2Py) at the propar-gylic position affords a breadth of vinyl silanes in good yields and excellent regio- and stereocontrol under mild conditions. The directing SO2Py group is essential in terms of reaction efficiency and chemoselectivity. Importantly, this group also provides the ability to reverse the regiochemical outcome of the reaction, opening the access to either regioisomer without modification of the starting substrate by virtue of an in situ base-promoted alkyne to allene equilibration which takes place prior to the silylcupration process. Furthermore, removal of the directing SO2Py allows for further elaboration of the silylation products. In particular, a one-pot tandem alkyne silylation/allylic substitution sequence, in which both steps are catalyzed by the same Cu species, opens up a new approach for the access to either formal hydrosilylation regioisomer of unsymmetrical aliphatic-substituted internal alkynes from propargyl sulfones This work was supported by the Ministerio de Economía y Com-petitividad (MINECO, CTQ2012-35790) and the European Union for a Marie Curie Career Integration Grant (to P.M). J. R. and P.M. thank MINECO for a FPI predoctoral fellowship and a Ramón y Cajal contract, respectively |
| Databáze: | OpenAIRE |
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