Conformational Transferability of the Sulfenyl Carbonyl Group −SC(O)– in Cyclic Thioesters

Dugarte, Nahir; Erben, Mauricio F.; Hey‐Hawkins, Evamarie; Lönnecke, Peter; Stadlbauer, Sven; Ge, Maofa; Yao, Li; Piro, Oscar E.; Echeverría, Gustavo A.; Védova, Carlos O. Della

doi:10.1021/jp4045308

Cited by 8 publications

(9 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Although much less pronounced, also ɛ-TnCL shows a rise in ΔH p compared to ɛ-CL (Table 3, entries 11-12). The same trend was observed by Dugarte et al [104][105][106][107] and Suzuki et al [63] when calculating and comparing ring strain energies of lactones and thiolactones by means of DFT (Table 4). Both types exhibit the same trend of the ring strain energy significantly dropping from four to five-membered rings and subsequently increasing from five to seven-membered rings.…”

Section: Thermodynamicssupporting

confidence: 80%

Sustainable Polythioesters via Thio(no)lactones: Monomer Synthesis, Ring‐Opening Polymerization, End‐of‐Life Considerations, and Industrial Perspectives

Narmon

Slagmaat²,

Wildeman³

et al. 2023

ChemSusChem

View full text Add to dashboard Cite

As the environmental effects of plastics are of ever greater concern, the industry is driven towards more sustainable polymers. Besides sustainability, our fast‐developing society imposes the need for highly versatile materials. Whereas aliphatic polyesters (PEs) are widely adopted and studied as next‐generation biobased and (bio)degradable materials, their sulfur‐containing analogs, polythioesters (PTEs), only recently gained attention. Nevertheless, the introduction of S atoms is known to often enhance thermal, mechanical, electrochemical, and optical properties, offering prospects for broad applicability. Furthermore, thanks to their thioester‐based backbone, PTEs are inherently susceptible to degradation, giving them a high sustainability potential. The key route to PTEs is through ring‐opening polymerization (ROP) of thio(no)lactones. This Review critically discusses the (potential) sustainability of the most relevant state‐of‐the‐art in every step from sulfur source to end‐of‐life treatment options of PTEs, obtained through ROP of thio(no)lactones. The benefits and drawbacks of PTEs versus PEs are highlighted, including their industrial perspective.

show abstract

Section: Thermodynamicssupporting

confidence: 80%

Sustainable Polythioesters via Thio(no)lactones: Monomer Synthesis, Ring‐Opening Polymerization, End‐of‐Life Considerations, and Industrial Perspectives

Narmon

Slagmaat²,

Wildeman³

et al. 2023

ChemSusChem

View full text Add to dashboard Cite

show abstract

“…An example is given in Figure with the X-ray crystal structure of a thiodepsipeptide AIP-4 analogue. Thus, once thiolactones are sufficiently large and unstrained to enable both types of conformations, these structures preferentially adopt the syn conformation as in low molecular weight acyclic thioesters. − …”

Section: Peptide Thioesters and Peptide Selenoesters: General Propert...mentioning

confidence: 99%

Native Chemical Ligation and Extended Methods: Mechanisms, Catalysis, Scope, and Limitations

et al. 2019

View full text Add to dashboard Cite

The native chemical ligation reaction (NCL) involves reacting a C-terminal peptide thioester with an N-terminal cysteinyl peptide to produce a native peptide bond between the two fragments. This reaction has considerably extended the size of polypeptides and proteins that can be produced by total synthesis and has also numerous applications in bioconjugation, polymer synthesis, material science, and micro-and nanotechnology research. The aim of the present review is to provide a thorough mechanistic overview of NCL and extended methods. The most relevant properties of peptide thioesters, Cys peptides, and common solvents, reagents, additives, and catalysts used for these ligations are presented. Mechanisms, selectivity and reactivity are, whenever possible, discussed through the insights of computational and physical chemistry studies. The inherent limitations of NCL are discussed with insights from the mechanistic standpoint. This review also presents a palette of O,S-, N,S-, or N,Se-acyl shift systems as thioester or selenoester surrogates and discusses the special molecular features that govern reactivity in each case. Finally, the various thiol-based auxiliaries and thiol or selenol amino acid surrogates that have been developed so far are discussed with a special focus on the mechanism of long-range N,S-acyl migrations and selective dechalcogenation reactions.

show abstract

“…In this study, the calculated strain energy was observed to be 6.38 kcal/mol from MP2 calculations and 5.69 kcal/mol with the M06-2X functional. Several reports have pointed out that the strain energies of cyclic molecules are influenced by heteroatom substitution or functionalization. − Thus, our results are comparable to these reports. The influence of substitution with the halogen atoms is quite minimal when compared to the heteroatom effect on the CHP ring.…”

Section: Results and Discussionmentioning

confidence: 96%

Meta-Hybrid Density Functional Theory Prediction of the Reactivity, Stability, and IGM of Azepane, Oxepane, Thiepane, and Halogenated Cycloheptane

et al. 2022

View full text Add to dashboard Cite

The application of plain cycloalkanes and heterocyclic derivatives in the synthesis of valuable natural products and pharmacologically active intermediates has increased tremendously in recent times with much attention being paid to the lower cycloalkane members. The structural and molecular properties of higher seven-membered and nonaromatic heterocyclic derivatives are less known despite their stable nature and vast application; thus, an insight into their structural and electronic properties is still needed. Appropriate quantum chemical calculations utilizing the ab initio (MP2) method, meta-hybrid (M06-2X) functional, and long-range-separated functionals (ωB97XD) have been utilized in this work to investigate the structural reactivity, stability, and behavior of substituents on cycloheptane (CHP) and its derivatives: azepane, oxepane, thiepane, fluorocycloheptane (FCHP), bromocycloheptane (BrCHP), and chlorocycloheptane (ClCHP). Molecular global reactivity descriptors such as Fukui function, frontier molecular orbitals (FMOs), and molecular electrostatic potential were computed and compared with lower members. The results of two population methods CHELPG and Atomic Dipole Corrected Hirshfeld Charges (ADCH) were equally compared to scrutinize the charge distribution in the molecules. The susceptibility of intramolecular interactions between the substituents and cycloalkane ring is revealed by natural bond orbital analysis and intramolecular weak interactions by the independent gradient model (IGM). Other properties such as atomic density of states, intrinsic bond strength index (IBSI), and dipole moments are considered. It is acclaimed that the strain effect is a major determinant effect in the energy balance of cyclic molecules; thus, the ring strain energies and validation of spectroscopic specificities with reference to the X-ray crystallographic data are also considered.

show abstract

Conformational Transferability of the Sulfenyl Carbonyl Group −SC(O)– in Cyclic Thioesters

Cited by 8 publications

References 55 publications

Sustainable Polythioesters via Thio(no)lactones: Monomer Synthesis, Ring‐Opening Polymerization, End‐of‐Life Considerations, and Industrial Perspectives

Sustainable Polythioesters via Thio(no)lactones: Monomer Synthesis, Ring‐Opening Polymerization, End‐of‐Life Considerations, and Industrial Perspectives

Native Chemical Ligation and Extended Methods: Mechanisms, Catalysis, Scope, and Limitations

Meta-Hybrid Density Functional Theory Prediction of the Reactivity, Stability, and IGM of Azepane, Oxepane, Thiepane, and Halogenated Cycloheptane

Contact Info

Product

Resources

About