The Ni‐Mediated Cyclocarbonylation of Allyl Halides and Alkynes Made Catalytic. Evidence Supporting the Involvement of Pseudoradical Ni¹ Species in the Mechanism.

Abstract

Mechanism. -(NADAL, M. L.; BOSCH, J.; VILA, J. M.; KLEIN, G.; RICART, S.; MORETO*, J. M.; J.

Cyclopentadienyl Rhenium (Technetium) Tricarbonyl Complexes Integrated in Estrogen Receptor Ligands for ER+ Tumor Imaging

“…A recent report describes a catalytic intermolecular 2+2+1 cyclization to form cyclopentenones using allyl bromide. 1 This variation on the Puason-Khand Reaction (PKR) does not suffer from the substrate limitations inherent in the PKR, as well as providing the essential methylene in a 1,3 relationship to the protected phenol. Initial cyclization provides the cyclopentenone acid 15, which eliminates to form cross-conjugated dienone 16 under decarboxylation conditions.…”

Nickel-catalyzed allylic carbonylative coupling of alkyl zinc reagents with tert-butyl isocyanide

“…At the outset of our investigation, we recognized several issues that needed to be addressed in order to develop an effective nickel-catalyzed allylic carbonylation. First, the use of nickel catalysts in carbonylation reactions has been less explored likely due to the strong binding affinity of CO towards nickel [39][40][41][42][43][44][45][46][47][48][49][50][51][52][53] . As a rare example, the Skrydstrup group elegantly succeeded the catalytic carbonylation of primary benzylic electrophile using a nickel pincer complex with a CO-gen precursor via the slow addition of Negishi reagent to circumvent the direct Negishi coupling, although the use of allyl electrophiles received limited success with 8% ketone formation 51 .…”