5 years ago

Sequential Reactions of Alkynes on an Iridium(III) Single Site

Sequential Reactions of Alkynes on an Iridium(III) Single Site
Elena A. Giner, Carmen Ramírez de Arellano, Luis Casarrubios, Alba D. Merinero, Miguel A. Sierra, Mar Gómez-Gallego
Sequential insertion of terminal alkynes on IrIII cyclometalated complexes allow the formation of novel metallapolycycles in a controlled and efficient manner. ortho-Methylarylethynyl derivatives led to an unprecedented cascade combination of three fundamental processes (C−C bond formation, C(sp3)−H activation, and reductive coupling) on a single IrIII center, in a process compatible with functionalized biomolecules and photoactive substrates. The reaction with tert-butylacetylene led to a [6,5,4]-polycycle that incorporates an iridacyclobutenylidene in its structure. The sequence is a multicomponent reaction in which the metal not only promotes the different steps but also determines their stereoselectivity. This is an elegant example of the synergy between a metal-promoting reaction and a symmetry-defined stereochemistry. La inserción secuencial de alquinos terminales en metalaciclos de IrIII permite la formación de nuevos tipos de metalapoliciclos de forma eficiente y controlada. Los ariletinil derivados orto-metil sustituidos dan lugar a la combinación en cascada de tres reacciones fundamentales sobre el mismo centro metálico de IrIII: formación de enlace C−C, activación de enlace C(sp3)-H y acoplamiento reductivo, en un proceso sin precedentes en la bibliografía. El proceso es compatible con biomoléculas funcionalizadas y compuestos fotoactivos. Por otra parte, la reacción de tert-butilacetileno conduce a la formación de un sistema policíclico [6,5,4] que incorpora un iridaciclobutenilideno en su estructura. La secuencia es una reacción multicomponente en la que el metal promueve no solo las diferentes etapas de reacción sino también su esteroselectividad. Este proceso es un elegante ejemplo de sinergia entre una reacción promovida por un centro metálico y una estereoquímica definida por la simetría. On your iridacycle! Cyclometalated half-sandwich IrIII complexes react with ortho-methyl-substituted aromatic alkynes to form Ir metallacycles resulting from the consecutive assembly of three efficient reactions: C−C bond formation, C(sp3)−H activation, and reductive coupling. The reaction is straightforward and allows for the incorporation of biomolecules (purines), photoactive molecules, and hybrid BODIPY–nucleoside derivatives, and as such are potentially useful for bio-labeling.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201701100

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