Thioamides as Useful Synthons in the Synthesis of Heterocycles

Jagodziński, T. S.

doi:10.1002/chin.200317242

Cited by 13 publications

(14 citation statements)

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“…The existence of Pd II -monoaminocarbene complexes 20 and the success of above reactions prompted us to expand this catalytic system to more general thioamide-containing substrates. Thioamides can be easily obtained by different functional group transformation, meanwhile, they also serve as versatile building blocks to provide valuable compounds 54 . Conventionally, Lawesson's reagent and its analogues are employed to the synthesis of thioamides, starting from aryl amides, aryl carboxylic acids, and nitriles 55 .…”

Section: Resultsmentioning

confidence: 99%

Palladium-catalyzed Suzuki-Miyaura coupling of thioureas or thioamides

Mai

et al. 2019

Nat Commun

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Cross-coupling reactions involving metal carbene intermediates play an increasingly important role in C-C bond formation. Expanding the carbene precursors to a broader range of starting materials and more diverse products is an ongoing challenge in synthetic organic chemistry. Herein, we report a Suzuki-Miyaura coupling reaction of in situ-generated Pd-carbene complexes via desulfurization of thioureas or thioamides. This strategy enables the preparation of a broad array of substituted amidinium salts and unsymmetrical diaryl ketones. The reaction is readily scalable, compatible with bromo groups on aromatic rings, tolerant to moisture and air and has a broad substrate scope. Furthermore, a single crystal structure of Pd-diaminocarbene complex is obtained and proven to be the key intermediate in both catalytic and stoichiometric reactions. Preliminary mechanistic studies demonstrate the dual role of the silver salt as a desulfurating reagent assisting the elimination of sulfur and as oxidant facilitating the Pd II /Pd 0 /Pd II catalytic cycle.

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Section: Resultsmentioning

confidence: 99%

Palladium-catalyzed Suzuki-Miyaura coupling of thioureas or thioamides

Mai

et al. 2019

Nat Commun

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“…Thioamides and their derivatives are an important class of molecules due to their use in synthetic chemistry, especially in the preparation of sulfur-containing heterocycles such as thiazoles and thioazolines. 56 Their utility stems in part from the presence of both nucleophilic and electrophilic reactive centers in their structures. In this work we employed the reversible addition− fragmentation chain transfer (RAFT) polymerization technique to synthesize macromolecular structures.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Macromolecular Hydrogen Sulfide Donors Trigger Spatiotemporally Confined Changes in Cell Signaling

et al. 2015

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Hydrogen sulfide (H2S) is involved in a myriad of cell signaling processes that trigger physiological events ranging from vasodilation to cell proliferation. Moreover, disturbances to H2S signaling have been associated with numerous pathologies. As such, the ability to release H2S in a cellular environment and stimulate signaling events is of considerable interest. Herein we report the synthesis of macromolecular H2S donors capable of stimulating cell signaling pathways in both the cytosol and at the cell membrane. Specifically, copolymers having pendent oligo(ethylene glycol) and benzonitrile groups were synthesized, and the benzonitrile groups were subsequently transformed into primary aryl thioamide groups via thionation using sodium hydrosulfide. These thioamide moieties could be incorporated into a hydrophilic copolymer or a block copolymer (i.e., into either the hydrophilic or hydrophobic domain). An electrochemical sensor was used to demonstrate release of H2S under simulated physiological conditions. Subsequent treatment of HEK293 cells with a macromolecular H2S donor elicited a slow and sustained increase in cytosolic ERK signaling, as monitored using a FRET-based biosensor. The macromolecular donor was also shown to induce a small, fast and sustained increase in plasma membrane-localized PKC activity immediately following addition to cells. Studies using an H2S-selective fluorescent probe in live cells confirmed release of H2S from the macromolecular donor over physiologically relevant time scales consistent with the signaling observations. Taken together, these results demonstrate that by using macromolecular H2S donors it is possible to trigger spatiotemporally confined cell signaling events. Moreover, the localized nature of the observed signaling suggests that macromolecular donor design may provide an approach for selectively stimulating certain cellular biochemical pathways.

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“…Over the past decade, β-ketothioamides (KTAs) acting as versatile synthons have received considerable attention and experienced very rapid development. 1 Having multiple active centers, KTAs are used not only as dinucleophilic reagents (Figure 1, types A−C) but also as dielectrophilic reagents in numerous reactions (Figure 1, type D), displaying a powerful ability for the construction of functionalized heterocyclic compounds. 2 Although intensive research efforts have been made in KTA chemistry, to date, the asymmetric reactions based on KTAs are still very rare with only few examples reported.…”

Section: ■ Introductionmentioning

confidence: 99%

Participation of β-Ketothioamides in N-Heterocyclic Carbene-Catalyzed [3 + 3] Spiroannulation: Asymmetric Synthesis of Functionalized Spiro-piperidinone Derivatives

Tan

Zhang

et al. 2018

J. Org. Chem.

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An N-heterocyclic carbene-catalyzed asymmetric [3 + 3] spiroannulation of β-ketothioamide was successfully developed. β-Ketothioamides exhibit an unusual reactivity to undergo a previously challenging lactamization reaction, and the desired spiro-piperidinone derivatives containing two vicinal stereogenic centers were synthesized in good to high yields with high stereoselectivities, whose structure can be converted to the corresponding imide and δ-lactam derivatives smoothly.

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Thioamides as Useful Synthons in the Synthesis of Heterocycles

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 13 publications

References 1 publication

Palladium-catalyzed Suzuki-Miyaura coupling of thioureas or thioamides

Palladium-catalyzed Suzuki-Miyaura coupling of thioureas or thioamides

Macromolecular Hydrogen Sulfide Donors Trigger Spatiotemporally Confined Changes in Cell Signaling

Participation of β-Ketothioamides in N-Heterocyclic Carbene-Catalyzed [3 + 3] Spiroannulation: Asymmetric Synthesis of Functionalized Spiro-piperidinone Derivatives

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