Easy synthesis and ring‐opening polymerization of 5‐Z‐amino‐δ‐valerolactone: New degradable amino‐functionalized (Co)polyesters

Abstract

Novel 5-Z-amino-d-valerolactone (5-NHZ-VL) was synthesized with an aim to prepare degradable polyesters and copolyesters having amino pendant groups. Following a straightforward and efficient synthetic pathway, 5-NHZ-VL was obtained in only two steps and up to 50% yield. The monomer was fully characterized by 1 H NMR, 13 C NMR, ESI mass spectrometry, and HPLC. Various conventional conditions were tested for this lactone ring-opening polymerization and led to the novel corresponding poly(5-NHZ-VL) (M n ¼ 7000 g/mol; PD ¼ 1.2). Following this homopolymerization, 5-NHZ-VL was copolymerized with e-caprolactone to generate a family of copolyesters with an amino-group content ranging from 10 to 80%. Finally, the polyelectrolyte poly(5-NH 3 þ -VL) was recovered by removal of the protecting group under acidic conditions, and integrity of the polyester backbone was confirmed by 1 H NMR. V C 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 5891-5898, 2010

From Polyesters to Polyamides Via ON Acyl Migration: An Original Multi‐Transfer Reaction

“…In our study, the N ‐benzyloxycarbonyl poly(L)serine ester ( 2a ) was obtained in one‐step by mesyl chloride activation of Z‐Ser‐OH in basic condition as previously described 20. We also included in our study the recently described poly(N‐Z‐γhhSer) (PγhhSZ, 2b ) 21…”

“…Their polymerization is usually performed from N‐carboxyanhydrides that need to be safely produced 16. Amino‐functionalized lactones as precursors for polymerization of hydroxyl‐amino acids such as serine or related compounds have also been described 17–21…”

Iterative Photoinduced Chain Functionalization as a Generic Platform for Advanced Polymeric Drug Delivery Systems

“…In fact, classical polyesters that are approved by the Food & Drug Administration for medical devices or drug formulations, like PLA, poly(glycolide) (PGA), PCL, and their copolymers, do not exhibit functional groups with exception to the terminal hydroxyl or carboxyl groups. To solve this lack of reactivity, various methods have been implemented including postpolymerization methods like wet chemistry under mild degrading conditions (aminolysis, hydrolysis) or plasma activation, and synthesis of lactones bearing functional groups . However, the postpolymerization strategies generally face problems of chain degradation and limited number of accessible reactive groups, whereas the lactone strategy faces problems of low yield due to multistep reactions and challenging purifications and, depending on the substituent, moderate to low monomer conversion and polymerization degrees.…”

Synthesis and characterization of α‐amino acid‐containing polyester: poly[(ε‐caprolactone)‐co‐(serine lactone)]

“…This has prompted several groups to explore functional monomers to copolymerize with CL. Monomers with ketone groups, azide groups, halide groups, hydroxyl groups and amino groups, have been successfully developed with a view to introducing their functional groups to PCL. However, in most cases, the synthesis of the functional monomers is a complicated and time‐consuming task, sometimes including several steps of column chromatography purification.…”

“…In addition to an investigation into the ring‐opening copolymerization of γCABεCL with CL so as to get amino‐functional PCL, they have also reported two block copolymers based on the ring‐opening polymerization of γCABεCL and γCABεCL with CL using monomethoxy‐poly(ethylene glycol) as macro‐initiator . The second monomer is 5‐ Z ‐amino‐δ‐valerolactone (5‐NHZ‐VL) which was explored by Nottelet's team. The copolymerization of 5‐NHZ‐VL with CL gave polyesters with aminated units ranging from 12 to 83% and molecular weights up to 8300 Da.…”