Nickel-catalyzed Thioester Transfer Reaction with sp²-Hybridized Electrophiles

Abstract

We report a thioacylation transfer reaction based on nickel-catalyzed C–C bond cleavage of thioesters with sp2-hybridized electrophiles. Aryl bromides, iodides, and alkenyl triflates can participate in thioester transfer reaction of aryl thioesters, affording a wide range of structurally diverse new thioesters in yields of up to 98% under mild reaction conditions. With this protocol, it is possible to construct alkenyl thioesters from the corresponding ketones through the generation of alkenyl triflates.

Nickel‐Catalyzed Synthesis of Thioesters from Amides and Disulfides

“…In 2020, Wu et al developed an interesting nickel‐catalyzed thiocarbonylation of arylboronic acids with sulfonyl chlorides to construct the thioesters using Mo(CO) 6 as solid CO surrogate (Scheme 1a) [8a] . Xie and co‐workers reported thioester transfer reaction catalyzed by nickel catalyst in 2022 (Scheme 1b) [8b] . In 2023, Liang et al developed a nickel‐catalyzed reductive coupling of carboxylic acids with disulfides to access thioesters under mild conditions (Scheme 1c) [8c] .…”

Ni-Catalyzed Aryl Thioester Synthesis via Thioester Transfer Reaction

“…In 2020, Yamaguchi et al [11] demonstrated a Ni-catalyzed aryl exchange reaction between aryl halides and aromatic esters to access new ester. In 2022, in the process of writing this paper, Xie et al [12] reported the synthesis of thioesters using nickel catalysis.…”

Transition-metal-free four-component reaction of nitriles and disulfides/diselenides

“…13 Recently, Huang and coworkers reported LiHMDS-promoted trimerization and dimerization of mixed nitriles under microwave radiation-free conditions (Scheme 1, path d). 14 On the other hand, organochalcogens display various chemical and biological properties, 15 thus the installation of a chalcogen-containing moiety into the 4-aminopyrimidine scaffolding would be very meaningful for new drug discovery. 16 In connection with our efforts on organochalcogen chemistry, 17 we disclose a four-component reaction of nitriles and disulfides/diselenides in the presence of t -BuOK and K 2 S 2 O 8 , offering a straightforward synthetic route to sulfurized/selenated 4-aminopyrimidines.…”