Gold (I/III)‐Catalyzed Trifluoromethylthiolation and Trifluoromethylselenolation of Organohalides

Abstract

The first CÀ SCF 3 /SeCF 3 cross-coupling reactions using gold redox catalysis [(MeDalphos)AuCl], AgSCF 3 or Me 4 NSeCF 3 , and organohalides as substrates are reported. The new methodology enables a one-stop shop synthesis of aryl/alkenyl/alkynyl trifluoromethylthio-and selenoethers with a broad substrate scope (> 60 examples with up to 97 % isolated yield). The method is scalable, and its robustness is evidenced by the late-stage functionalization of various bioactive molecules, which makes this reaction an attractive alternative in the synthesis of trifluoromethylthio-and selenoethers for pharmaceutical and agrochemical research and development.

Site-Selective Arylation of Carboxamides from Unprotected Peptides

“…The commercially available dipeptide alanylglutamine with a free carboxylic acid was selectively functionalized at the amide position to furnish a product (31) in a yield of 71%. The peptide drug molecules protirelin and taltirelin with imidazole residues underwent arylation exclusively at the carboxamide site (32,33), and no arylation at the backbone amide group was observed. 17 Other tripeptide and tetrapeptide substrates were also tested and gave rise to the corresponding products (34−37) in moderate to good yields.…”

“…In recent years, homogeneous gold-catalyzed cross-coupling transformations − have exhibited excellent functional group tolerance and biocompatibility within aqueous reaction media. These unique features of gold catalysis offer a new opportunity for the late-stage modification (LSM) of peptides. , In 2019, Patil and coworkers have reported the first ligand-enabled gold-catalyzed arylation of a range of amines and amides with aromatic iodides .…”

Density Functional Theory Study of Gold-Catalyzed 1,2-Diarylation of Alkenes: π-Activation versus Migratory Insertion Mechanisms

“…13−15 In recent years, other strategies like strain release, 16,17 ligand design, 18,19 and photoredox catalysis 20 have been greatly developed to promote oxidant-free Au I /Au III catalysis. 21−23 By using these strategies, Hashmi et al, 24 Bourissou et al, 25−28 Patil et al, 29−31 Hammond et al, 32 and Shi et al 33 have made great progress in the cross-coupling reactions of carbon− carbon or carbon−heteroatom bonds.…”