Nickel‐Catalyzed Coupling of Arylzinc Halides with Thioesters

Abstract

The Pd-catalyzed Fukuyama reaction of thioesters with organozinc reagents is a mild, functional-group-tolerant method for acylation chemistry. Its Ni-catalyzed variant might be a sustainable alternative to expensive catalytic Pd sources. We investigated the reaction of S-ethyl thioesters with aryl zinc halides with hetero- and homotopic Ni precatalysts and several ligands. The results show that both homo- and heterotopic species may contribute to catalysis. The substrate scope using an operationally homogeneous defined Ni complex was established. Acyl radicals are postulated as short-lived intermediates.

Cross-Coupling of Chloro(hetero)arenes with Thiolates Employing a Ni(0)-Precatalyst

“…18 During our study on the Ni-catalyzed Fukuyama coupling, we observed a MR of chloroarenes resulting from the liberated zinc thiolate. 19 Herein, this Ni-catalyzed side reaction was studied in more detail, which resulted in the discovery of an efficient catalytic system for the MR of chloroarenes (Scheme 1b). It operates at exceptionally low catalyst loading and mild conditions compared to competitive Ni-based catalysts.…”

A Nickel(II)‐Mediated Thiocarbonylation Strategy for Carbon Isotope Labeling of Aliphatic Carboxamides

“…This rapid and quantitative formation of the 2-pyridyl thioester from crystalline and nontoxic 2,2'-dipyridyl disulfide providesaconvenient and easy route for the synthesis of an active ester.B esides serving as viable acylation reagents for amidations, the 2-pyridyl thioesters are also reactive towards a variety of carbon-centered nucleophiles and exploitedi nt he Corey-Nicolaoum acrolactonization and the Fukuyama ketone synthesis. [23] Am echanism similar to that proposed for reaction of the Ni II -acyl complex with activatedalkyl halides is proposed andillustrated in Scheme 6. [18] Single electront ransfer from nickel(II) to the disulfide resultsi nt he abstraction of ap yridylthiyl fragment formingaNi III (SPy)(acyl) complex and the generation of a thiyl radical.…”

ORCHEM Prizes: I. Fleischer and F. Beuerle / Emil Fischer Medal: T. Bach / Leonidas Zervas Award: C. P. R. Hackenberge / Hanwha‐Total IUPAC Young Scientist Award: A. Walther / Thieme–IUPAC Prize: S. Herzon / Greifswald Research Award: U. T. Bornscheuer / Melvin Calvin Award: T. Skrydstrup

“…Fleischer's research focuses on homogeneous catalysis and synthetic methodology, especially in the chemistry of C−S bonds. She has reported in Chemistry—A European Journal on the nickel‐catalyzed coupling of arylzinc halides with thioesters …”