Biosynthetic routes to both enantiomers of biphenyl cis-2,3- and cis-3,4-dihydrodiols from biphenyl. BPDO, biphenyl dioxygenases from Pseudomonas sp. LB400 or S. yanoikuyae B8/36 form 100% (+)-biphenyl cis-(2R,3S)-dihydrodiol; CDO; carbazole dioxygenase from P. stutzeri C250 forms >95% (−)-biphenyl cis-(2S,3R)-dihydrodiol; TDO, toluene dioxygenase from P. putida UV4 and four synthetic steps (Fig. 1 and Materials and Methods) resulted in 100% (+)-biphenyl cis-(3R,4S)-dihydrodiol; the F352V mutant of NDO and toluene cis-dihydrodiol dehydrogenase (TDD) from P. putida F1, followed by one purification step, resulted in 100% (−)-biphenyl cis-(3S,4R)-dihydrodiol.