Synthesis of Macrocyclic Oligomers of Pivalolactone. Crystal Structure and Properties of Tetrolide

Matuszowicz, Andrzej; Jedliński, Zbigniew; Gawron, Marian; Kosturkiewicz, Z.

doi:10.1021/jo00126a036

Cited by 3 publications

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“…One of the most reactive catalytic systems for the polymerization of lactones is anionic ring-opening polymerization (AROP). AROP dates back to 1961 with the polymerization of ß-propiolactone and has since been used to polymerize a variety of different small-sized enthalpy-driven cyclic ester monomers such as lactides, − ε-caprolactone (εCL), ,− δ-valerolactone (δVL), , β-butyrolactone(s) (βBL), ,− pivalolactone, , undecanolide and dodecanolide, and even the entropy driven and strainless macrocyclic ω-pentadecalactone (PDL) . Well-defined architectures such as block copolymers based on small-ring-sized lactones such as εCL, δVL, and βBL have also been reported. ,,,− …”

Section: Introductionmentioning

confidence: 99%

Mastering Macromolecular Architecture by Controlling Backbiting Kinetics during Anionic Ring-Opening Polymerization

Nieboer,

Fanjul-Mosteirín,

Olsén

et al. 2024

Macromolecules

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Defined macromolecular architecture using anionic ring-opening copolymerization (ROcP) of lactones and cyclic carbonates offers facile routes toward copolymers with unique material properties, ranging from thermoplastic to elastomeric. However, monomers with a slow ROP rate are hampered by competing backbiting reactions, scrambling the macromolecular sequence, and, thereby, a loss of material properties occurs. We here solve this issue by controlling the rate of backbiting. Through our approach, we show how block structures previously inaccessible can be synthesized from monomers with vastly different ROP rates, covering small lactones and even including macrolactones. This control can also be extended beyond block structures to include random and gradient architectures by tuning monomer concentration to the relative ROP and backbiting rate.

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Section: Introductionmentioning

confidence: 99%

Mastering Macromolecular Architecture by Controlling Backbiting Kinetics during Anionic Ring-Opening Polymerization

Nieboer,

Fanjul-Mosteirín,

Olsén

et al. 2024

Macromolecules

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“…5). It turned out that these compound are already known, and the crystal-structure of 24 has been published previously [57]. They have been prepared by oligomerisation of 3-hydroxy-2,2-dimethylpropionolactone 25.…”

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confidence: 99%

An Unexpected Formation of a 14‐Membered Cyclodepsipeptide

Iliev

Linden

Heimgartner

2003

Helvetica Chimica Acta

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The treatment of diluted solutions of the hydroxy diamides 6a and 6b in toluene with HCl gas at 100°gave the dimeric, 14-membered cyclodepsipeptide 10 in up to 72% yield (Scheme 3). The same product was formed from the linear dimer of 6b, the depsipeptide 11, under the same conditions (cf. Scheme 4). All attempts to prepare the cyclic seven-membered monomer 9, starting with different precursors and using different lactonization methods failed, and 10 was the only product which was isolated (cf. Scheme 6). For example, the reaction of the ester 20 with NaH in toluene at 80°led exclusively to the cyclodimer 10. On the other hand, the base-catalyzed cyclization of the hydroxy diester 22, which is the 'O-analogue' of 20, yielded neither the seven-membered dilactone, nor the 14-membered tetralactone, but only the known trimer 23 and tetramer 24 of 2,2-dimethylpropano-3-lactone (cf. Scheme 7). 2The treatment of diluted solutions of the hydroxydiamides 6a and 6b in toluene with HCl gas at 100 o gave the dimeric, 14-membered cyclodepsipeptide 10 in up to 72% yield (Scheme 3).The same product was formed from the linear dimer of 6b, the depsipeptide 11, under the same conditions (Scheme 4). All attempts to prepare the cyclic 7-membered monomer 9, starting with different precursors and using different lactonization methods failed, and 10 was the only product which was formed (Scheme 6). For example, the reaction of the ester 20 with NaH in toluene at 80 o led exclusively to the cyclodimer 10. On the other hand, the base catalyzed cyclization of the hydroxydiester 22, which is the 'O-analogue' of 20, yielded neither the 7-membered dilactone, nor the 14-membered tetralactone, but only the known trimer 23 and tetramer 24 of 2,2-dimethylpropiolactone (Scheme 7).3

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Anionic polymerization of pentadecanolide. A new route to a potentially biodegradable aliphatic polyester

Jedliński

Juzwa

Adamus

et al. 1996

Macro Chemistry & Physics

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The anionic polymerization of pentadecanolide ( 1 -oxa-2-cyclohexadecanone) initiated with potassium alkoxides was investigated. Polymerization proceeds under mild conditions (tetrahydrofuran, 35 "C ) to form high-molecular-weight polymer (number-average molecular weight a,, up to 100000). The formation of cyclic oligomers, via back-biting reaction, was demonstrated by means of gel-permeation chromatography (GPC) and matrix assisted laser desorption ionisation-time of flight (MALDI-TOF) analyses.

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Synthesis of Macrocyclic Oligomers of Pivalolactone. Crystal Structure and Properties of Tetrolide

Cited by 3 publications

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Mastering Macromolecular Architecture by Controlling Backbiting Kinetics during Anionic Ring-Opening Polymerization

Mastering Macromolecular Architecture by Controlling Backbiting Kinetics during Anionic Ring-Opening Polymerization

An Unexpected Formation of a 14‐Membered Cyclodepsipeptide

Anionic polymerization of pentadecanolide. A new route to a potentially biodegradable aliphatic polyester

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