Hydrozirconation of Thioketones. A Simple, Convenient Entry into a Variety of Organosulfur Compounds. An Intersting Ether Synthesis

Article abstract of DOI:10.1021/jo00315a012

Aromatic and aliphatic thioketones undergo hydrozirconation at room temperature with (C5H5)2Zr(H)Cl to give sulfur-zirconium compounds, R2CHSZr(Cl)(C5H5)2.Cleavage of the latter by bromine or N-bromosuccinimide affords sulfenyl bromides, acid chlorides give thioesters, methyloxalyl chloride gives a thiooxalate, methyl vinyl ketone results in the formation of the β-keto sulfide, and carbonylation followed by bromination in alcohol affords the ether.Yery mild conditions are utilized for all of these reactions.Mechanisms are proposed for the interesting ether synthesis.