Theoretical and experimental studies of 1,5,7-triazabicyclo[4.4.0]dec-5-ene-catalyzed ring opening/ring closure reaction mechanism for 5-, 6- and 7-membered cyclic esters and carbonates

Nifant’ev, Ilya E.; Shlyakhtin, Andrey V.; Bagrov, Vladimir V.; Lozhkin, Boris A.; Zakirova, Gladis G.; Ivchenko, Pavel V.; Legonkova, O.A.

doi:10.1007/s11144-015-0952-y

Cited by 21 publications

(17 citation statements)

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“…Thus, TBD, in combination with the ROH initiator, catalyzed the ROP of moderately strained lactones and lactide acting as an acid and base simultaneously, activating both cyclic ester and ROH via the formation of two hydrogen bonds. Our scientific group performed a detailed study of TBD-catalyzed ROP of 5-, 6-and 7-membered cyclic esters and carbonates [94] at B3LYP/6-311G(d) [39,40,51,98] level of theory while using methanolysis as a model reaction. First, we calculated the geometries of the reaction complexes that formed by TBD, trimethylene carbonate (TMC), and MeOH and found that TBD-MeOH complex can be considered as a common ground state for all of the processes under study (Figure 19).…”

Section: Tbd Substituted Guanidines and Related Compoundsmentioning

confidence: 99%

“…The changes of free energies are given in kcal/mol. The colored version of the figure presented in[94]. Copyright (2015) Springer Nature.…”

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confidence: 99%

“…Energy profiles obtained by DFT calculations for TBD-catalyzed ring-opening methanolysis of trimethylene carbonate (TMC) for mechanisms A (red) and B (green). The colored version of the figure presented in[94]. Copyright (2015) Springer Nature.…”

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confidence: 99%

“…DFT modeling of TBD-catalyzed methanolysis of (a) 5-, 6-, and 7-membered cyclic carbonates and (b) γBL, δVL, εCL, polymerizability of 1,4-dioxan-2-one (PDO), and glycolide (GL). The colored version of the figure presented in[94]. Copyright (2015) Springer Nature.…”

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confidence: 99%

“…∆G -ln k i correlation in TBD-catalyzed ROP/transesterification. The colored version of the figure presented in[94]. Copyright (2015) Springer Nature.…”

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confidence: 99%

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DFT Modeling of Organocatalytic Ring-Opening Polymerization of Cyclic Esters: A Crucial Role of Proton Exchange and Hydrogen Bonding

Nifant’ev

Ivchenko

2019

Polymers

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Organocatalysis is highly efficient in the ring-opening polymerization (ROP) of cyclic esters. A variety of initiators broaden the areas of organocatalysis in polymerization of different monomers, such as lactones, cyclic carbonates, lactides or gycolides, ethylene phosphates and phosphonates, and others. The mechanisms of organocatalytic ROP are at least as diverse as the mechanisms of coordination ROP; the study of these mechanisms is critical in ensuring the polymer compositions and architectures. The use of density functional theory (DFT) methods for comparative modeling and visualization of organocatalytic ROP pathways, in line with experimental proof of the structures of the reaction intermediates, make it possible to establish these mechanisms. In the present review, which continues and complements our recent manuscript that focused on DFT modeling of coordination ROP, we summarized the results of DFT modeling of organocatalytic ROP of cyclic esters and some related organocatalytic processes, such as polyester transesterification. 4 of 49 were found to be polymerizable due to strain in the ester group. In addition, the predominance of high-energy coiled conformations in linear homopolymers the formed from PDO, εCL and GL was proportionately less than extended conformations, in comparison to the inactive monomer γBL. However, while the prevalence of coiled conformations over extended conformations was expected for poly(LA), this factor does not affected the reactivity of lactides. Very good agreement between the experimental and calculated data for ROP of GL, l-LA and (R,S)-lactide [47] should be separately noted. 4-(Dimethylamino)pyridine (DMAP) and Related CompoundsDMAP was the first employed organocatalyst in polymer synthesis. In 2001, Nederberg et al. [48] reported the "first organocatalytic living polymerization" (Ð M < 1.2) of L-lactide (l-LA) mediated by DMAP or 4-pyrrolidinopyridine in the presence of ROH initiators. Four years later [49], Feng and Dong reported polymerization of ε-caprolactone (εCL) catalyzed by DMAP in the presence of chitozane as an initiator. Bourissou et al. studied the mechanism of DMAP-catalyzed ROP of l-LA and five-membered lactic O-carboxylic anhydride (lacOCA) [50]. Two possible reaction pathways were analyzed at the B3LYP/6-31G(d) level of theory [39,40,51]; the solvent effect of dichloromethane was taken into account through the PCM/SCRF model [52]. The modeled reaction was the methanolysis of l-LA or lacOCA; alternative nucleophilic/monomer (Scheme 1a) and basic/alcohol (Scheme 1b) activation mechanisms were proposed for these reactions, and then analyzed by DFT optimization of the key reaction intermediates and transition states, if necessary. Scheme 1. Schematic representation of the nucleophilic/monomer (a) and basic/alcohol (b) mechanisms for (Dimethylamino)pyridine (DMAP)-catalyzed methanolysis of l-LA. Author Contributions: Conceptualization, P.I.; Methodology, I.N. and P.I.; Writing-Original draft preparation, P.I.; Writing-Review and editing, I.N. and P.I.; V...

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Section: Tbd Substituted Guanidines and Related Compoundsmentioning

confidence: 99%

“…The changes of free energies are given in kcal/mol. The colored version of the figure presented in[94]. Copyright (2015) Springer Nature.…”

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

“…∆G -ln k i correlation in TBD-catalyzed ROP/transesterification. The colored version of the figure presented in[94]. Copyright (2015) Springer Nature.…”

mentioning

confidence: 99%

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DFT Modeling of Organocatalytic Ring-Opening Polymerization of Cyclic Esters: A Crucial Role of Proton Exchange and Hydrogen Bonding

Nifant’ev

Ivchenko

2019

Polymers

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Triazabicyclodecene: A versatile catalyst for polymer synthesis

Kim,

Lee,

Lee

2023

Journal of Polymer Science

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This comprehensive review aims to provide an in‐depth analysis of the catalytic performance of 1,5,7‐triazabicyclo[4,4,0]dec‐5‐ene (TBD) in polymer synthesis. TBD, a well‐established organic superbase, possesses a distinctive bifunctional character that grants it exceptional capabilities, particularly in processes such as transesterification or transamidation. TBD has garnered considerable attention since its initial report by Hedrick and Waymouth in 2006, and it has played a pivotal role in diverse polymerization reactions. Its versatility spans various polymerization modes, including chain‐growth and step‐growth polymerization, post‐polymerization modification, and network thermoset formation. More recently, its utility has extended to the green chemical recycling of polymers. By providing an encompassing overview of TBD's historical journey, this review delves into its past accomplishments while shedding light on its present and future potential to organocatalysts in polymer science.

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Sorbitol-based aqueous cyclic carbonate dispersion for waterborne nonisocyanate polyurethane coatings via an environment-friendly route

Dai

Tang

et al. 2018

J Coat Technol Res

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Theoretical and experimental studies of 1,5,7-triazabicyclo[4.4.0]dec-5-ene-catalyzed ring opening/ring closure reaction mechanism for 5-, 6- and 7-membered cyclic esters and carbonates

Cited by 21 publications

References 61 publications

DFT Modeling of Organocatalytic Ring-Opening Polymerization of Cyclic Esters: A Crucial Role of Proton Exchange and Hydrogen Bonding

DFT Modeling of Organocatalytic Ring-Opening Polymerization of Cyclic Esters: A Crucial Role of Proton Exchange and Hydrogen Bonding

Triazabicyclodecene: A versatile catalyst for polymer synthesis

Sorbitol-based aqueous cyclic carbonate dispersion for waterborne nonisocyanate polyurethane coatings via an environment-friendly route

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