1391069-26-3Relevant academic research and scientific papers
Acyl-carbene and methyl-carbene coupling via migratory insertion in palladium complexes
Meana, Isabel,Albeniz, Ana C.,Espinet, Pablo
, p. 5494 - 5499 (2012/11/07)
The migratory insertion reaction of a carbene into a palladium-acyl bond has been observed both for monoaminocarbenes and for methoxycarbenes. The acyl derivative [PdCl(COMe){C(NEt2)Ph}(PPh3)] undergoes an acyl-carbene coupling, leading to the enolate-type complex [PdCl{C(COMe) (NEt2)Ph}(PPh3)]2 (2). This complex decomposes either by reductive elimination to give the iminium salt or by protonation of the enolate to give a ketoamine. In a similar fashion, the reaction of [Pd 2(μ-Cl)2(COMe)2(SMe2) 2] with [W(CO)5{C(OMe)Ph}] leads to an undetected palladium enolate that, after protonation, is stabilized by coordination to palladium ([PdCl2{(OH)MeC=CPh(OMe}(SMe2)], 8). The reaction of [Pd2(μ-Cl)2Me2(SMe 2)2] with [W(CO)5{C(OMe)-Ph}] leads to the migratory insertion of the carbene into the Pd-methyl group to give an alkyl palladium complex. The transfer of CO from tungsten, followed by insertion into the Pd-Me group, also occurs. This leads to the formation of a Pd-COMe group, which also undergoes migratory insertion of the carbene fragment. These results support that migratory insertion is a key C-C coupling step, as proposed for the new Pd-catalyzed transformations that use carbene precursors.
