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Título

Conclusive evidence on the mechanism of the rhodium-mediated decyanative borylation

AutorEsteruelas, Miguel A. ; Oliván, Montserrat ; Vélez, Andrea
Fecha de publicación2015
EditorAmerican Chemical Society
CitaciónJournal of the American Chemical Society 137(38): 12321-12329 (2015)
ResumenThe stoichiometric reactions proposed in the mechanism of the rhodium-mediated decyanative borylation have been performed and all relevant intermediates isolated and characterized including their X-ray structures. Complex RhCl{xant(PiPr2)2} (1, xant(PiPr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) reacts with bis(pinacolato)diboron (B2pin2), in benzene, to give the rhodium(III) derivative RhHCl(Bpin){xant(PiPr2)2} (4) and PhBpin. The reaction involves the oxidative addition of B2pin2 to 1 to give RhCl(Bpin)2{xant(PiPr2)2}, which eliminates ClBpin generating Rh(Bpin){xant(PiPr2)2} (2). The reaction of the latter with the solvent yields PhBpin and the monohydride RhH{xant(PiPr2)2} (6), which adds the eliminated ClBpin. Complex 4 and its catecholboryl counterpart RhHCl(Bcat){xant(PiPr2)2} (7) have also been obtained by oxidative addition of HBR2 to 1. Complex 2 is the promoter of the decyanative borylation. Thus, benzonitrile and 4-(trifluoromethyl)benzonitrile insert into the Rh–B bond of 2 to form Rh{C(R-C6H4)═NBpin}{xant(PiPr2)2} (R = H (8), p-CF3 (9)), which evolve into the aryl derivatives RhPh{xant(PiPr2)2} (3) and Rh(p-CF3-C6H4){xant(PiPr2)2} (10), as a result of the extrusion of CNBpin. The reactions of 3 and 10 with B2pin2 yield the arylBpin products and regenerate 2.
DescripciónThis is an open access article published under an ACS AuthorChoice License.
Versión del editorhttp://dx.doi.org/10.1021/jacs.5b07357
URIhttp://hdl.handle.net/10261/122840
DOI10.1021/jacs.5b07357
ISSN0002-7863
E-ISSN1520-5126
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