Synthesis of Thioamides

Murai, Toshiaki

doi:10.1007/978-981-13-7828-7_3

Cited by 18 publications

(27 citation statements)

References 89 publications

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“…[25][26][27] Furthermore, thioamides have become attractive as photoswitches enabling trans to cis isomerization owing to red-shifted π!π* transition, [28][29][30][31] while affinity of the sulfur atom to certain metals in thioamides has found applications in the development of new coordination complexes. [32] Furthermore, the presence of thioamides in natural products and recent studies indicating posttranslational thioamidation by Nature, [11,12] highlight the role of thioamides as one of the most fundamental amide-derived linkages in chemistry.…”

Section: Introductionmentioning

confidence: 99%

Chemoselective Transamidation of Thioamides by Transition‐Metal‐Free N−C(S) Transacylation

Xing

Zhao

et al. 2022

Angewandte Chemie

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Thioamides represent highly valuable isosteric in the strictest sense “single‐atom substitution” analogues of amides that have found broad applications in chemistry and biology. A long‐standing challenge is the direct transamidation of thioamides, a process which would convert one thioamide bond (R−C(S)−NR1R2) into another (R−C(S)−NR3N4). Herein, we report the first general method for the direct transamidation of thioamides by highly chemoselective N−C(S) transacylation. The method relies on site‐selective N‐tert‐butoxycarbonyl activation of 2° and 1° thioamides, resulting in ground‐state‐destabilization of thioamides, thus enabling to rationally manipulate nucleophilic addition to the thioamide bond. This method showcases a remarkably broad scope including late‐stage functionalization (>100 examples). We further present extensive DFT studies that provide insight into the chemoselectivity and provide guidelines for the development of transamidation methods of the thioamide bond.

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Section: Introductionmentioning

confidence: 99%

Chemoselective Transamidation of Thioamides by Transition‐Metal‐Free N−C(S) Transacylation

Xing

Zhao

et al. 2022

Angewandte Chemie

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“…1–7 In contrast with the carbonyl group, 8,9 the π bond inside CS exhibits good reactivity, which results from the poor orbital overlap between carbon and sulfur owing to their distinctly different size. 10 Thionoesters are regarded as synthetic isosteres of esters 11–13 and have been readily employed as precursors to construct diverse organic compounds. 14,15 For example, thionoesters fluorinated by DAST or Deoxofluor can directly give access to the corresponding α,α-difluoroethers in good yields under mild conditions, 16–18 attributable to the higher electrophilicity relative to their oxoester counterparts (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

An efficient and straightforward approach for accessing thionoesters via palladium-catalyzed C–N cleavage of thioamides

Liu

Irfan

et al. 2022

Org. Biomol. Chem.

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“…The ligand can act as mono and dianionic ligand depending on the nature of solvent, central backbone and base added into the medium [15]. Moreover, the protonation-deprotonation of the secondary thioamide group and the hydrogen bonding between NH and any H-bond acceptor have a profound effect on the structure, properties as well as reactivities of the related complexes [16][17][18].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Photophysical Properties and Catalytic Activity of Ƙ3-SCS Pincer Palladium (II) Complex of N,N'-Di-Tert-Butylbenzene-1,3-Dicarbothioamide Supported by DFT Analysis

Das¹,

Kannan²,

Kumar³

et al. 2021

Preprint

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The title complex [PdCl(L)] (1), is obtained from the reaction of SCS pincer ligand HL (where, HL = N,N'-di-tert-butylbenzene-1,3-dicarbothioamide) with lithium tetrachloropalladate (II) in methanol. The compound 1 is characterized by elemental analysis, FTIR, 1H, and 13C-NMR spectroscopy, UV-Vis spectroscopy, powder X-ray diffraction and X-ray crystallographic techniques. At room temperature, 1 emits luminescence light of wavelength 460 nm in the solid state upon excitation by UV light of wavelength 280 nm. The average emission lifetime indicates that, both the ligand and complex emission is fluorescence in nature and involves mainly ligand centers π-π* deexcitation. It also shows good catalytic activity towards Mizoroki-Heck and Suzuki-Miyaura cross-coupling reactions of aryl bromides with tert-butyl acrylate and p-tolylboronic acid respectively. For both type of reactions, more than 99% conversion of the substrates is found to occur for electronically activated p-nitro bromobenzene using 1 mol % of 1. Further, modern DFT calculations are performed to decipher the mechanistic insight on the preferable pathways of the Mizoroki-Heck cross-coupling reaction. Stepwise free energy of reactions for various probable reaction pathways suggest that the catalytic route has profound preference for Pd(0)-Pd(II) over Pd(II)-Pd(IV) pathway.<br>

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Synthesis of Thioamides

Cited by 18 publications

References 89 publications

Chemoselective Transamidation of Thioamides by Transition‐Metal‐Free N−C(S) Transacylation

Chemoselective Transamidation of Thioamides by Transition‐Metal‐Free N−C(S) Transacylation

An efficient and straightforward approach for accessing thionoesters via palladium-catalyzed C–N cleavage of thioamides

Synthesis, Photophysical Properties and Catalytic Activity of Ƙ3-SCS Pincer Palladium (II) Complex of N,N'-Di-Tert-Butylbenzene-1,3-Dicarbothioamide Supported by DFT Analysis

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