Reagent-controlled regiodivergent resolution of unsymmetrical oxabicyclic alkenes using a cationic rhodium catalyst.

A Rh(I) catalyzed regiodivergent addition of heteroatom nucleophiles to racemic oxabicyclic alkenes produces good yields of regioisomeric products each in high ee. Powerful reagent control is demonstrated, as the inherent reactivity of the substrate is completely dominated by the chiral catalyst complex, which is shown to require the use of cationic Rh(I). The process affords rapid access to multiple 1,2-dihydronapthalene products in high enantioselectivity from simple starting materials.