A (MeDalphos)AuCl complex was found to efficiently catalyze the cross-coupling of indoles and allyl acetates/alcohols. The reaction tolerates many functional groups and selectively affords the branched C3-allylated products from both αand γ-substituted allyl substrates. It takes the advantage of the hemilabile character of the P ∧ N ligand. The C(sp 2 )−C(sp 3 ) coupling operates via a Au(I)/ Au(III) redox cycle and involves a dicationic π-allyl Au(III) complex as a key intermediate. In this case, the allyl moiety adopts an asymmetric σ + π-coordination mode, as substantiated by NMR spectroscopy and density functional theory (DFT) calculations.
Discovered as organometallic curiosities in the 1970s,
carbene
radicals have become a staple in modern-day homogeneous catalysis.
Carbene radicals exhibit nucleophilic radical-type reactivity orthogonal
to classical electrophilic diamagnetic Fischer carbenes. Their successful
catalytic application has led to the synthesis of a myriad of carbo-
and heterocycles, ranging from simple cyclopropanes to more challenging
eight-membered rings. The field has matured to employ densely functionalized
chiral porphyrin-based platforms that exhibit high enantio-, regio-,
and stereoselectivity. Thus far the focus has largely been on cobalt-based
systems, but interest has been growing for the past few years to expand
the application of carbene radicals to other transition metals. This
Perspective covers the advances made since 2011 and gives an overview
on the coordination chemistry, reactivity, and catalytic application
of carbene radical species using transition metal complexes and catalysts.
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