Chemistry of the β-Thiolactones: Substituent and Solvent Effects on Thermal Decomposition and Comparison with the β-Lactones.

Noel, Amandine; Delpech, Bernard; Crich, David

doi:10.1021/jo500577c

Cited by 12 publications

(15 citation statements)

References 85 publications

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“…Several reports have pointed out that the strain energies of cyclic molecules are influenced by heteroatom substitution or functionalization. 32 − 35 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 Discussionsupporting

confidence: 92%

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

et al. 2022

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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.

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Section: Results and Discussionsupporting

confidence: 92%

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

et al. 2022

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“…Further control experiments demonstrated that thiolactone 49 can be converted into alkene 50 by prolonged heating under reflux in ethanol although this thermal reaction did not proceed as cleanly as the photochemical olefination process. Interest in the thermal decomposition process has gained further interest in recent years [34] . A similar result was obtained for the reaction of N ‐methyldithiophthalimide 51 with the ketene (using equal equivalents of each reagent), although more dethiocarboylation product was obtained.…”

Section: Intramolecular Radical Routes For Thiolactone Synthesissupporting

confidence: 54%

Radical‐Mediated Approaches for the Synthesis of Thiolactones

McCourt

Scanlan

2021

Eur J Org Chem

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In this review we discuss the diverse synthetic approaches and methodologies which have been utilized for the preparation of small and medium ring thiolactones via radical‐mediated processes. We provide a brief overview of the major current applications and uses of thiolactones in disparate fields of study and outline a selection of representative methods which have been employed for the preparation of compounds containing this structural motif, with a concise consideration of the conditions employed, the key intermediates formed and the mechanism of the transformations, where pertinent. Reaction classification has been broadly divided into two distinct classes: those in which the key bond forming step is an intermolecular radical process, and those in which it is an intramolecular process (radical cyclization). Both of these reaction classes may be further subdivided into processes that proceed via a carbon‐centered (C‐centered) radical, and those that proceed through a thiyl/sulfur‐centered (S‐centered) radical.

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“…Encouraged by this, thioester 2a was hydrolyzed to deprotect the thiol and carboxylic acid moiety, furnishing 5-mercaptopentanoic acid. The free thiol was then immediately subjected to Steglich cyclization conditions, modified slightly from conditions previously reported for the synthesis of β-thiolactones . To the thiol in anhydrous CH 2 Cl 2 under dilute conditions were added 2 equiv of the carbodiimide coupling reagent EDC·HCl and 1.2 equiv of the nucleophilic catalyst 4-(dimethylamino)pyridine (DMAP).…”

mentioning

confidence: 89%

“…Thiolactones represent an underexploited class of sulfur-containing heterocyclic compounds with potential application in numerous fields, although of late they have garnered increased interest. β-thiolactones, although somewhat unstable, have drawn considerable attention for their ability to mediate the coupling of sterically demanding peptides by native chemical ligation . γ-Thiolactones have proven useful in chemical biology, , medicinal chemistry, drug discovery, and materials science, , with the γ-thiolactones derivatives of homocysteine thiolactone (Hcy-thiolactone), the product of homocysteine metabolism, of particular interest (Figure ).…”

mentioning

confidence: 99%

A Sequential Acyl Thiol–Ene and Thiolactonization Approach for the Synthesis of δ-Thiolactones

McCourt

Scanlan

2019

Org. Lett.

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A novel strategy for the synthesis of δ-thiolactones from inexpensive and readily available γ-unsaturated esters has been developed. This strategy incorporates a radical acyl thiol–ene reaction as the key C–S bond forming step. Cyclization is achieved via a Steglich-type thiolactonization of 5-mercaptopentanoic acids. We report the facile and scalable synthesis of δ-thiolactones in moderate to good yield under mild reaction conditions with tolerance for a range of functional groups.

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Chemistry of the β-Thiolactones: Substituent and Solvent Effects on Thermal Decomposition and Comparison with the β-Lactones.

Cited by 12 publications

References 85 publications

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

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

Radical‐Mediated Approaches for the Synthesis of Thiolactones

A Sequential Acyl Thiol–Ene and Thiolactonization Approach for the Synthesis of δ-Thiolactones

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