ENANTIOSELECTIVE CATALYSIS .111. NEW CHIRAL EXPANDED PHOSPHANES DERIVED FROM SUBSTITUTED DELTACYCLENES

The suitability of enantiomerically pure deltacyclenes as building blo cks in the synthesis of expanded phosphanes was examined. Different su bstituted deltacyclenes were irradiated with diphenylphosphane and thr ee bisphosphanyl derivatives. With these P-H addition reactions, new c hiral deltacyclane-derived phosphorus ligands were synthesized. They w ere tested in the Rh-catalyzed asymmetric hydrogenation of (Z)-(alpha) -N-acetamidocinnamic acid and in the Pd-catalyzed asymmetric allylatio n of 1,5-dimethylbarbituric acid.