The free cis-diol metabolite (1) produced from the oxidation of bromobenzene by Pseudomonas putida underwent Pd(0)-catalyzed coupling with trimethylsilyl acetylene, phenylacetylene and 1-hexyne providing the novel homochiral (1S, 2R)-3-alkynyl cis-cyclohexa-3,5-diene-1,2-diols 2-4 in good to excellent yields.