Lipase-catalyzed polymerization of fluorinated lactones and fluorinated hydroxycarboxylic acids

Runge, Martina; O’Hagan, David; Haufe, Günter

doi:10.1002/(sici)1099-0518(20000601)38:11<2004::aid-pola90>3.0.co;2-t

Cited by 35 publications

(27 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Partial racemate cleavage was also observed in lipasecatalyzed polycondensation of this type of fluorohydrins [159]. Kinetic resolution of 1-fluoro-oct-7-en-2-ol was accomplished by lipase-catalyzed acetylation with Candida antarctica lipase (CAL, Novozyme 1 435) and vinyl acetate in cyclohexane to obtain the (R)-(þ)-fluorohydrin and the (S)-(À)-2-acetoxy-1-fluoro-oct-7-ene both with high enantiomeric excess (Scheme 66) [98].…”

Section: Resolution Of Racemic Vicinal Fluorohydrins Using Enzyme-catmentioning

confidence: 69%

See 1 more Smart Citation

Regio- and stereoselective synthesis of vicinal fluorohydrins

Haufe

2004

Journal of Fluorine Chemistry

View full text Add to dashboard Cite

Section: Resolution Of Racemic Vicinal Fluorohydrins Using Enzyme-catmentioning

confidence: 69%

“…We selectively synthesized several more regioisomeric terminal fluorohydrins either by ring opening with Olah's reagent or KHF 2 in the presence of a crown ether [96][97][98][99][100].…”

Section: Synthesis By Nucleophilic Ring Opening Of Epoxidesmentioning

confidence: 99%

Regio- and stereoselective synthesis of vicinal fluorohydrins

Haufe

2004

Journal of Fluorine Chemistry

View full text Add to dashboard Cite

“…The much lower polymerizability of 2c is probably due to the lower reactivity of the terminal secondary alcohol, which nucleophilically attacks onto the acyl carbon of the acyl-enzyme intermediate in the propagation stage. 5a The molecular weight of poly(2a) was larger than that of the polymer from 2b or 2d under the similar reaction conditions (entries [8][9][10][11][12][13][14][15][16].…”

Section: Comparison Of Enzymatic Ring-opening Polymerizability Betweementioning

confidence: 94%

“…Fluorinecontaining lactones were also enantioselectively polymerized by lipase CA catalyst. 10 In order to systematically examine the enzymatic polymerizability of unsubstituted and substituted lactones, we have performed the lipase-catalyzed polymerization of various substituted lactones. Furthermore, the enzymatic polymerizability of these lactones has been compared with that by an anionic initiator.…”

mentioning

confidence: 99%

Lipase-Catalyzed Ring-Opening Polymerization of Substituted Lactones

Kikuchi

Uyama

Kobayashi

2002

Polym J

View full text Add to dashboard Cite

ABSTRACT:Effects of substituted position and ring size of methyl-substituted lactones in their lipase-catalyzed polymerization have been systematically investigated. In the polymerization of 6-and 7-membered lactones using Candida antarctica lipase as catalyst, the reaction behaviors of α-substituted lactones were relatively similar to those of the unsubstituted ones, whereas much lower enzymatic polymerizability was observed in the case of ω-substituted lactones. The enzymatic polymerization of γ-methyl-ε-caprolactone also proceeded under mild reaction conditions and the reaction rate was close to that of ε-caprolactone. In the polymerization of α-methyl-substituted macrolides (13-and 16-membered), the polymerizability decreased by the introduction of the methyl substituent. The enzymatic polymerizability of these lactones was compared with their anionic polymerizability using sodium methoxide as initiator. In case of all the α-or ω-substituted lactones examined, the lower anionic polymerizability was observed than that of the unsubstituted ones. These data indicate that the polymerization behaviors strongly depended on the lactone ring size and substituent position as well as type of catalyst (initiator).KEY WORDS Enzymatic Polymerization / Lactone / Lipase / Polyester / Ring-Opening Polymerization / Ring-opening polymerization of lactones has been extensively studied, since it provides a facile synthetic route of biodegradable polyesters with controlled structure and molecular weight. 1 So far, a variety of catalysts have been developed for the precise polymerization of lactones. Recently, lipase has received much attention as new catalyst for production of biodegradable polyesters. 2 Lipase catalyzed ring-opening polymerization of unsubstituted lactones in various ring-sizes under mild reaction conditions, yielding high molecular weight polyesters. 3 Furthermore, lipase catalysis exhibited unusual polymerizability of lactones in comparison with that of conventional chemical catalysts. Our recent report showed that macrolides possessed much lower reactivity in the polymerization catalyzed by zinc octanoate than δ-valerolactone (1a) or ε-caprolactone (2a). 4 In the Pseudomonas fluorescens lipase-catalyzed polymerization, on the other hand, the reverse tendency was observed. 5 This is due to the stronger recognition of the macrolides by lipase catalyst.So far, there have been many studies concerning ring-opening polymerization of various 4-membered substituted lactones by chemical catalysts. 1a Lipase also induced the polymerization of such lactones, 6 and the enantioselection took place to give optically active polyesters under selected conditions. 6b,6d,6e In contrast, the ring-opening polymerization of sub- † To whom correspondence should be addressed. stituted lactones of other ring sizes using chemical catalysts has little been reported.For example, α-n-propyl-δ-valerolactone and δ, δ-dimethyl-δ-valerolactone showed no polymerizability using sodium catalyst. 7 Aluminum isopropoxide catalyst polymerize...

show abstract

“…However, no information on the degree of enantioselectivity of the polymerization was given. Partially fl uorine -substituted lactones have been enantioselectively polymerized as well [37] .…”

Section: Krp Of Substituted Lactonesmentioning

confidence: 99%