Enantioselectivity effects in the hydrolytic cleavage of activated substrates with α- and β-cyclodextrins

Abstract
The kinetics of hydrolytic cleavage of the enantiomers of p- and m-nitrophenyl (Np) phenylacetate esters of general structure PhCR1R2–CO2–Np where R1,R2= H,Me [(1), (2)], H,OMe [(3), (4)], or CF3,OMe [(5), (6)], and of the carbonates PhCHMe–OCO2p-Np (7) and n-C6H13–CHMe–OCO2p-Np (8), have been measured in the presence of α- and β-cyclodextrins. The rates of intracomplex cleavage were found to be larger for the R- than for the S-enantiomers in almost all cases; the enantioselectivity factors range from unity to ca. 19 depending on the relative size of the pairs of substituents R1 and R2. The effects have been interpreted with the help of molecular models.

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