Benzocyclic compounds are also found in important biologically active substances. In particular, the ,-dimethyl substituent is the backbone found in synthetic analogs of retinoic acid. For example, all-trans-retinoic acid exhibits a wide variety of activities owing to its flexible structure and has been linked to toxicity and teratogenicity. Synthetic analogs called arotinoids (,dimethyl-substituted benzocyclic compounds) have been designed including bexarotene (cutaneous T-cell lymphoma), tazarotene (acute promyelocytic leukemia), and tamivarotene (acne and psoriasis). Given this background, we examined a method for synthesizing benzocyclic compounds using the aromatic ring as the nucleophile in the MHAT/RPC mechanism. We treated alkenyl arenes 7a with complex C1, Me3NFPY•OTf, and (Me2SiH)2O in trifluorotoluene to produce chromane 8a in low yield (Table ); the low yield may be attributed to the formation of a trisubstituted alkene (53%) and hydrate (29%). After further optimization, when the diamine moiety of the cobalt catalyst was changed to 1,3-propanediamine (C9), the yield of 8a increased to 83%. This Schiff base ligand was particularly effective for the hydroarylation of disubstituted alkenes. Further catalyst optimization revealed that bulky substituents on the aromatic ring were essential for hydroalkoxylation and hydroamination (C9-C11).