New
methodology is presented for the formation of unsymmetrical
organotrisulfides in a high yield and purity, relatively free of polysulfide
byproducts. The highlight of the method is the low-temperature (−78
°C) deprotection of a disulfanyl acetate with sodium methoxide
in THF to form a disulfanyl anion, which reacts rapidly in situ with
an organothiosulfonate (S-aryl or S-alkyl) within 30 seconds followed by quenching. The discovery of
these new reaction conditions together with the relative greenness
of the chemistry overall makes for an efficient protocol, from which
a range of organotrisulfides covering aliphatic, aromatic, as well
as cysteine and sugar groups can be accessed in a high yield and purity.