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Anion-Dependent Switch in C–X Reductive Elimination Diastereoselectivity

[Image: see text] Reaction of a complex Pt organometallic species with electrophilic halogen sources in the presence of X(–) ligands changes the mechanism of reductive elimination from a concerted reductive coupling type to an S(N)2 type reductive elimination. In the absence of the added X(–) ligand...

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Detalles Bibliográficos
Autores principales: Geier, Michael J., Dadkhah Aseman, Marzieh, Gagné, Michel R.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2014
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4157736/
https://www.ncbi.nlm.nih.gov/pubmed/25221379
http://dx.doi.org/10.1021/om5006929
Descripción
Sumario:[Image: see text] Reaction of a complex Pt organometallic species with electrophilic halogen sources in the presence of X(–) ligands changes the mechanism of reductive elimination from a concerted reductive coupling type to an S(N)2 type reductive elimination. In the absence of the added X(–) ligand the reductive elimination is stereoretentive; in its presence, the process is stereoinvertive. This selectivity hinges on the reactivity of a key five-coordinate Pt(IV) intermediate with the X(–) ligand.