Catalysis ring-opening polymerization

Lipase catalysis is often used for enantioselective production of chiral compounds. Lipase induced the enantioselective ring-opening polymerization of racemic lactones. In the lipase-catalyzed polymerization of racemic (3-BL, the enantioselec-tivity was low an enantioselective polymerization of (3-BL occurred by using thermophilic lipase to give (/ )-enriched PHB with 20-37% enantiomeric excess (ee). ... 

Reactive polyesters were enzymatically synthesized. Lipase catalysis chemoselecfively induced the ring-opening polymerization of a lactone having exo-methylene group to produce a polyester having the reactive exo-methylene group in the main chain (Scheme 16). This is in contrast to the anionic... 

Polyester syntheses have been achieved by enzymatic ring-opening polymerization of lactide and lactones with various ring-sizes. Here, we focus not only on these cyclic esters but also other cyclic monomers for lipase-catalyzed ringopening polymerizations. Figure 8 summarizes cyclic monomers for providing polyesters via lipase catalysis. 

Ring-opening polymerization of a-methyl-substituted medium-size lactones, a-methyl-y-valerolactone and a-methyl-c-caprolactone, proceeded by using lipase CA catalyst in bulk [82]. As to (R)- and (S)-3-methyl-4-oxa-6-hexa-nolides (MOHELs), lipase PC induced the polymerization of both isomers. The apparent initial rate of the S-isomer was seven times larger than that of the R-isomer, indicating that the enantioselective polymerization of MOHEL took place through lipase catalysis [83]. 

For example, see Slomkowski, S. and Duda, A. Anionic ring-opening polymerization, In Ring-Opening Polymerization, Mechanisms, Catalysis, Structure, and Utility, Brunelle, D. J. (Ed.), Hanser-Verlag, New York, pp. 87-128, 1993. 

Al-Azemi TF, Kondaveti L, Bisht KS (2002) Solventless enantioselective ring-opening polymerization of substituted-caprolactones by enzymatic catalysis. Macromolecules 35 3380-3386... 

Slomkowski, S. and A. Duda, Anionic Ring-Opening Polymerization, Chap. 3 in Ring-Opening Polymerization. Mechanism, Catalysis, Structure, Utility, D. J. Brunelle, eds., Hanser, Munich, 1993. 

Extension of DKR to polymer chemistry would readily result in chiral polyesters, polycarbonates, or polyamides from an optically inactive monomer mixture. Scheme 10 describes three variants of chemoenzymatic catalysis applied in polymer chemistry that recently appeared in the literature. Route A uses AA and BB monomers to prepare chiral polymers from racemic/diasteromeric diols. Route B converts an enantiomer mixture of AB monomers to homochiral polymers. Route C is the enzymatic ring-opening polymerization of co-methylated lactones to homochiral polyesters. Details will be given in Sect. 3.4.2. 

Cyano compounds liquid crystals, 12, 278 in silver(III) complexes, 2, 241 Cyanocuprates, with copper, 2, 186 Cyano derivatives, a-arylation, 1, 361 Cyanosilanes, applications, 9, 322 Cyclic acetals, and Grignard reagent reactivity, 9, 53 Cyclic alkenes, asymmetric hydrosilylation, 10, 830 Cyclic alkynes, strained, with platinum, 8, 644 Cyclic allyl boronates, preparation, 9, 196 Cyclic allylic esters, alkylation, 11, 91 Cyclic amides, ring-opening polymerization, via lanthanide catalysis, 4, 145... 

Cyclic amino-carbenes, in molybdenum carbonyls, 5, 457 Cyclic bis(phosphine) dichlorides, with iron carbonyls, 6, 48 Cyclic carbenes, as gold atom ligands, 2, 289 Cyclic carbometallation, zirconium complexes, 10, 276 Cyclic carbozirconation characteristics, 10, 276 intermolecular reactions, 10, 278 intramolecular reactions, 10, 278 Cyclic dinuclear ylides, and gold , 2, 276 Cyclic 1,2-diols, intramolecular coupling to, 11, 51 Cyclic enones, diastereoselective cuprate additions, 9, 515 Cyclic esters, ring-opening polymerization, via lanthanide catalysis, 4, 145 Cyclic ethers... 

Ring-opening polymerization is one of the most important applications of SCBs in organic chemistry. Polymerization of SCBs, which gives rise to carbosilane polymers, has been carried out thermally, by transition metal catalysis, or, most commonly, by anionic initiation. Thermal polymerization is rare, however, and is not covered in this chapter. For leading references into thermal polymerization of SCBs, refer to <1996CF1EC-II(1B)867> and <1995COMC-II(2)50>. 

A series of water-dispersible, surface-active poly(fluorinated oxetane)s was prept sd by ring-opening polymerization of fluorinated oxetane monomers using Lewis acid catalysis <02L5993>. 

Construction of Al—O—Ln Motif for Ring-Opening Polymerization Catalysis... 

The first example of fully aqueous metal catalysis of olefin isomerization was reported by Grubbs et al. in 1994 [2]. These authors adopted [Ru(H20)6](tos)2 (tos = p-toluenesulfonate) [8] as a catalyst, which is highly active for the ring-opening polymerization of strained cyclic olefin. Both allylic alcohol and allylic ethers undergo isomerization in the presence of [Ru(H20)6](tos)2. 

This interpretation is supported by extension of this novel catalysis to cyclic olefins (32, 32a). Cyclic olefins undergo smooth ring-opening polymerization to polymers which are, in fact, massive ring polyenes of structure XVIII. 

Recently, norbornene was reported to undergo ring-opening polymerization in the presence of molybdenum, tungsten, and rhenium halide catalysts (33). In each of these studies (33-35), the catalysis was interpreted by mechanisms involving the scission of the carbon-carbon single bond adjacent to the double bond, e.g., Eq. (12). 

The subjects Include fundamental and applied research on the polymerization of cyclic ethers, slloxanes, N-carboxy anhydrides, lactones, heterocycllcs, azlrldlnes, phosphorous containing monomers, cycloalkenes, and acetals. Block copolymers are also discussed where one of the constituents is a ring opening monomer. Important new discussions of catalysis via not only the traditional anionic, cationic and coordination methods, but related UV Initiated reactions and novel free radical mechanisms for ring opening polymerization are also Included. 

Catalysis design for ring-opening polymerization of cyclic esters 1. Group 1 metal and thallium(I) trispyrazolylborate complexes with hemilabile ligands... 

Lipase-catalyzed synthesis of polyesters came to the focus after two major breakthroughs in 1984, novel lipase-catalyzed polycondensation to give oli-goesters in 1993, discovery of the catalysis for ring-opening polymerization of lactones. 

Uyama, H., Kobayashi, S., Morita, M., Habaue, S., and Okammoto, Y. (2001) Chemoselective ring-opening polymerization of a lactone having exo-methylene group with lipase catalysis. Macromolecules, 34 (19), 6554-6556. 

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