The thesis describes the development of a new reaction sequence wich transforms aromatic compounds into regio- and stereoselectively functionalized cyclohexadienes. This is achieved through a sequential nucleophile/electrophile addition across an arene double bond. Activation to the first C-C bond forming reaction is by complexation of the arene to an electrophilic transition metal complex fragment (Cr(CO)₃). Regioselectivity is controlled by an imine substituent which directs the incoming group highly selectively to an "ortho" carbon. This combination of the use of a chiral auxiliary with organometallic methodology is highly successful and provides the basis for efficient applications in synthesis. The second step involves metal alkylation or allytation and migration of this group to the 3-position of the polyene ligand. This takes place either directly or following migratory CO insertion. An asymmetric synthesis is provided by a chiral benzaldehyde hydrazone complex. In most cases only one of the two possible diastereomers is formed.