Abstract A very efficient enzymatic method was developed for the synthesis of new enantiomeric benzocispentacin and its six-and seven-membered homologues through the Lipolase (lipase B from Candida antarctica) catalyzed enantioselective (E> 200) ring opening of 3, 4-benzo-6-azabicyclo [3.2. 0] heptan-7-one, 4, 5-benzo-7-azabicyclo [4.2. 0] octan-8-one, and 5, 6-benzo-8-azabicyclo [5.2. 0] nonan-9-one with H 2 O in iPr 2 O at 60 ...