One-Pot Synthesis Of Chiral Disulfides & Diselenides From α-Amino Acids Mediated By Ammonium Tetrathiomolybdate In Water

Abstract

We have described herein a convenient one-pot synthesis of lisulfides/diselenides from a-amino acids mediated by ammonium etrathiomolybdate in water. (Figure 1) (Figure) Figure 1 Transformation of α-amino acids into the corresponding tiiocyanates/selenocyanates/disulfides/diselenides

Halo-de-amination of a-amino acids using HBr/NaNCte followed by treatment with ammonium tetrathiomolybdate (NH4)2]VloS4 jLb provided a general route for the the one-pot synthesis of chiral a,a' bis (dithio) carboxylic acids (Figure 1, 2b). The yields were moderate, limited mainly the moderate conversion of a-amino acids into the corresponding chiral a-bromides.

It was possible to synthesize the 2-thiocyanto carboxylic acids from the corresponding a-amino acids by a similar strategy. Thus diazotization in the presence of KSCN yielded in the chiral 2-thiocyanto carboxylic acids in moderate yields (Figure 1, 3). Thiocyanato-de-amination thus afforded the thiocyanates which when treated with JJD provided the chiral disulfides (Figure 1, 4a). We could thus synthesize both enantiomers of the disulfide from a single enantiomer of the starting a-amino acid. (Figure 1, 4a,4b) Using a similar strategy we have also demonstrated an efficient method for the synthesis of chiral selenocyanates starting from a-amino acids, using selenocyanate anion as the nucleophile (Figure 1, 5). It is possible to demonstrate a one-pot synthesis of chiral diselenides by reductive coupling of selenocyanates using JJb. (Figure 1, 6) (for figure see the pdf file)