Iodomethylthiobenzoate 5 and α-chloroalkyl phenyl sulfides 6 were found to insert zinc dust in THF under very mild conditions (10–25° C, 0.5–2 h) leading to zinc α-thioorganometallics. After a transmetallation with CuCN· 2 LiCl, the corresponding copper reagents 8 and 7 reacted with various electrophiles (1-haloalkynes, aldehydes, enones, acyl chlorides, allylic halides, trialkyltin halides) affording polyfunctional thioesters and sulfides of type 9 or 10 ...