Enzymatic polyesterification in organic media. II. Enzyme‐catalyzed synthesis of lateral‐substituted aliphatic polyesters and copolyesters

Abstract

Enzymatic polymerization of hydroxyesters in organic media has been the subject of a previous and ongoing research in our laboratory. As part of that study, four ϵ‐substituted‐ϵ‐hydroxyesters were synthesized, and then polymerized using crude porcine pancreatic lipase (PPL) in n‐hexane. These lateral‐substituted hydroxyesters polymerized enantioselectively to produce optically active oligomers and a resolved optically active unreacted monomer. It was found that with increasing bulkiness of the lateral substituent, in the order Me >Et >Ph, the enzymatic reaction becomes slower, yet the enantioselectivity is higher. The lateral‐substituted hydroxyesters were also copolymerized enzymatically with the more reactive linear methyl ϵ‐hydroxyhexanoate. Optically active copolymers were obtained, higher in molecular weight than the analogous homopolymers. © 1993 John Wiley & Sons, Inc.

Recent Developments in Lipase‐Catalyzed Synthesis of Polyesters

“…The enantioselectivity increased as a function of bulkiness of the monomer substituent. [145] Lipase Catalyst for Green Polymer Chemistry…”

Lipase-catalyzed ring-opening polymerization of 3(S)-isopropylmorpholine-2,5-dione

“…Examples are the first in vitro synthesis of cellulose by cellulase-catalyzed polymerization of b-cellobiosyl fluoride via a non-biosynthetic path way 5) , the first synthesis of chitin via chitinase-catalyzed polymerization of a chitobiose oxazoline derivative 6) , and a new class of polyphenols by peroxidase-catalyzed oxidative polymerization of various phenol derivatives 7,8) . Recently, enzymatic syntheses of aliphatic polyesters have been studied extensively 1,[8][9][10] . Medium-size lactones (6-and 7-membered) as well as macrocyclic lactones (12-, 13-, and 16-membered) were polymerized with a lipase as a catalyst under mild reaction conditions, yielding the corresponding polyesters [11][12][13][14][15][16][17][18][19][20][21][22] .…”

Enzymatic Synthesis of Polyesters via Polycondensation

“…HPLC analysis showed that the (R)-enantiomer possessed higher enzymatic reactivity. Optically active oligomers (DP < 6) were also synthesized from racemic ε-substituted-ε-hydroxy esters using PPL as catalyst [97]. The enantioselectivity increased as a function of bulkiness of the monomer substituent.…”