Optically active (+)-2-endo-acetoxy-5-endo-bornyl methacrylate (ABMA) was prepared from (+)-camphor. The free-radical homopolymerization of ABMA and its copolymerization with achiral methyl methacrylate (MMA) or styrene (St) were carried out with 2,2'-azoisobutyronitrile in benzene. Effects of temperature and reaction time on the copolymerization were discussed. The monomer reactivity ratios (r,, r2) for poly(ABMA-co-MMA) and poly(ABMA-co-St) as well as Q and e values for the chiral ABMA in the copolymerization systems were evaluated by the Fineman-Ross method. It was found that the absolute value of the specific rotation of poly(ABMA-co-MMA) increased with increasing ABMA unit content. A small deviation from linearity was observed, which suggests that asymmetry is not introduced into the copolymer main chain. Temperature and solvent effects on the specific rotation of the chiral homopolymer and copolymers were investigated. The results suggest that the chiral polymers synthesized in this investigation did not show a strong preference for a particular helical conformation. Applications of the chiral polymers on the asymmetric addition of nbutyllithium to aldehydes were investigated. The effect of temperature and aldehydes on the asymmetric addition were also discussed. ZUSAMMENFASSUNG:Optisch aktives ( + )-2-endo-Acetoxy-5-endo-bornylmethacrylat (ABMA) wurde aus (+)-Campher hergestellt und in Benzol radikalisch homo-bzw. mit achiralem Methylmethacrylat (MMA) bzw. Styrol (St) copolymerisiert. Der EinfluB von Temperatur und Reaktionszeit auf den Polymerisationsverlauf wird diskutiert. Die Copolymerisationsparameter (r, und r2, nach Fineman-Ross) fur Poly(ABMA-co-MMA) und Poly(ABMA-co-St) sowie die Q-und e-Werte fur ABMA wurden berechnet.Der Absolutwert der spezifischen Drehung von Poly(ABMA-co-MMA) nimmt mit steigendem ABMA-Gehalt im Copolymeren zu. Eine geringe Abweichung von der Linearitat deutet darauf hin, daB die Copolymerhauptkette nicht asymmetrisch ist. Aus der Temperatur-und Lijsungsmittelabhangigkeit der spezifischen Drehung der be-schriebenen Homo-und Copolymeren laBt sich schlierjen, da13 diese nicht in einer speziellen helikalen Konformation vorliegen. Die Eignung der chiralen Polymeren a k Katalysatoren fur die asymmetrische Addition von Butyllithium an verschiedene Aldehyde in Abhangigkeit von der Temperatur wurde untersucht.

SUMMARY:A series of bornane derivatives was synthesized. Both new chiral monomers ( + )-5,6-dioxobornyl methacrylate and ( + )-5,6-exo-dihydroxybornyl methacrylate were prepared from (+)-borneol. The free-radical polymerization of both new monomers was carried out at 60°C for 6 h in various organic solvents. The conversion of the polymerization was found to be affected by the kind of solvent, and the lowest conversion was attained in (-)-menthol.

Three types of chiral polymer containing dimethylaminobornane moieties were synthesized. The asymmetric addition of butyllithium to various aldehydes in the presence of chiral polymers as catalysts were carried out at different reaction temperatures. The highest enantiomeric excess (54,770) was achieved with the chiral homopolymer with a spacer inserted between the polymer chain and the dimethylaminobornane moiety. The chiral polymers can be easily separated from the reaction mixture and re-used.

SYNOPSISOptically active 2-endo-actoxy-5-endo-bornyl methacrylate ( ABMA) was prepared from (+) -camphor. The homopolymerization of ABMA and copolymerization of ABMA with achiral methyl methacrylate (MMA) or styrene (St) were carried out with 2,2'-azobisisobutyronitrile (AIBN) in benzene. Effects of temperature, solvents, and reaction time on the copolymerization were discussed. The monomer reactivity ratios ( rl, r z ) for poly (ABMAco-MMA) and poly(ABMA-co-St) and Q and e values for the chiral ABMA in the copolymerization systems were evaluated by the Fineman-Ross method. The absolute value of the specific rotation of poly ( ABMA-co-MMA) increased with increasing ABMA unit content. A small deviation from linearity was observed, which suggests that asymmetry is not introduced into the copolymer main chain. Temperature and solvent effects on the specific rotation of the chiral homopolymer and copolymers were investigated. The results suggest that the chiral polymers synthesized in this investigation did not show a strong preference for a particular helical conformation. Applications of the chiral polymers on the asymmetric addition of n -butyllithium to aldehydes were also discussed.

SynopsisA series of diastereoisomeric amino bicyclo [ 2,2,1] heptane derivatives was synthesized from ( + ) -camphor. Further treatment of aminobornanols with triethyl orthopropionate afforded chiral oxazolines, which were found to be efficient for the asymmetric induction of carboxylic acids. Synthesis and polymerization of the new chiral oxazolinebornyl methacrylate derived from aminobornanols was carried out. Effects of temperature, solvents, and molar ratio of the reagent on the polymerization of the linear chiral polymers and the synthesis of the insoluble chiral crosslinked polymers were also discussed. Aminobornanols and chiral polymers with pendant aminobornanol moieties were found to be efficient for the asymmetric induction of chiral metbylalkanoic acids. Recovery of the chiral reagents, the stereoselectivity of chiral oxazolines, and the parameters governing its successful implementation and the mechanistic aspects of the processes were also investigated.