ASYMMETRIC CATALYSIS - ASYMMETRIC CATALYTIC INTRAMOLECULAR HYDROACYLATION OF 4-PENTENALS USING CHIRAL RHODIUM DIPHOSPHINE CATALYSTS

Catalysts of the type [Rh(chiral diphosphine)](+) convert 4-substitute d 4-pentenals into the corresponding 3-substituted cyclopentanones wit h generally high turnover numbers and frequencies at 25 degrees C. The enantioselectivities of various substituted 4-pentenals with two chir al diphosphines have been explored. It was found that with the binap c atalyst, almost complete enantioselectivity is observed for 4-pentenal substrates bearing 4-substituted tertiary substituents and for ester groups. Ketonic substituents give very high enantioselectivities. The mechanism of intramolecular hydroacylation has been explored, and it i s suggested that an important consideration for obtaining high turnove r frequencies is related to the acyl-alkyl reductive elimination mecha nism which is inferred to occur by a process similar to ester hydrolys is. The origin of the enantioselection is discussed in terms of the in teractions between the phenyl groups of the phosphine and the substitu ent of the pentenal.