Recent advances in the Willgerodt–Kindler reaction

Priebbenow, Daniel L.; Bolm, Carsten

doi:10.1039/c3cs60154d

Cited by 151 publications

(87 citation statements)

References 89 publications

(58 reference statements)

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“…Multicomponent polymerizations (MCPs), as an emerging field of polymer chemistry, display a series of advantages such as high efficiency, mild reaction conditions, atom economy, and operational simplicity and thus are representing a powerful new approach for the preparation of functional polymers. Willgerodt–Kindler type reactions of dialdehydes and diamines in the presence of sulfur were investigated for preparation of polythioamides (Scheme C) . The one‐pot, three‐component polycondensation developed by Kanbara and co‐workers afforded various polythioamides in moderate to good yields depending on the adopted reaction conditions.…”

Section: Chemistrymentioning

confidence: 99%

Sulfur Chemistry in Polymer and Materials Science

Mutlu

Ceper

et al. 2018

Macromol. Rapid Commun.

278

220

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The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/marc.201800650. ChemistryBefore moving to the recent advances within the last 5 years in the diverse applications of sulfur chemistry in polymer and Sulfur-Containing PolymersSulfur and its functional groups are major players in an area of exciting research taking place in modern polymer and materials science, both in academia and industry. In fact, manifold sulfur-based reactions that are both exceptionally versatile as well as tremendously useful have been implemented, and further utilized for the design and preparation of polymeric materials that lead to a plethora of applications ranging from medicine to optics and nanotechnology to separation science. Hence, within this review, an overview of strategies and developments used over the last 5 years to reinforce the importance of the sulfur functional group in modern polymer and materials science is presented. In particular, many important references in the primary literature of sulfur chemistry are referred to, including thiol-ene, thiol-yne, thiol-Michael addition, disulfide cross-linking, and thiol-disulfide exchange, among others, by explaining and illustrating the important principles. Last but not least, the grand aim to underpin the importance of sulfur in modern polymer and materials science is achieved by presenting selected examples in diverse fields and postulating the respective potential for real-world applications. he is now a full professor at KIT.sulfur atoms, and tetraphenylethene-bearing di(alkyl bromide) (Scheme 3). The yield of the polymerization was dependent on the di(alkyl bromide) monomer; the longer spacer between the aromatic moiety and the reactive bromide end groups Scheme 1. The discussion henceforth focuses on the synthesis of polymers possessing the depicted sulfur functional groups. Scheme 2.Representative examples of polythioethers prepared via A) the nucleophilic substitution reaction between an electrophilic dihalide with nucleophilic derivatives of dithiols under alkaline conditions; B) the thiol-ene/yne addition reaction between AA and BB type monomers (i.e., dithiols and dienes/diynes); and C) radical or ionic ring-opening of sulfurcontaining strained rings.Scheme 3. The thiol-bromo polymerization of conformationally fixed monomers to provide multifunctional polymers. [19] Macromol. Rapid Commun. 2019, 40, 1800650 Scheme 4. The regioselective selective nucleophilic aromatic substitution between thiol and fluorinated aromatic compounds, the para-fluorothiol reaction (PFTR).Scheme 5. Synthesis of a linear polymer via PFTR-reaction. [21]

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Section: Chemistrymentioning

confidence: 99%

Sulfur Chemistry in Polymer and Materials Science

Mutlu

Ceper

et al. 2018

Macromol. Rapid Commun.

278

220

View full text Add to dashboard Cite

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“…Willgerodt-Kindler reaction is another alternative means to access thioamides, starting from different types of starting materials such as aryl aldehydes, aryl alkyl ketones, aryl amides, and aryl acetic acids in one step 56,57 . It means that these common compounds can conveniently be used to prepare diaryl ketones in two steps with our method, which can enlarge the accessible chemical space.…”

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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“…T hisw as due to the polysulfides generated by the cleavage of SÀSb onds when S 8 was under stepwise nucleophilic attack by amines. [12] Based on the control experiments and previous literature, [7,8,12] ap lausible mechanism is proposed in Scheme3, which begins with the nucleophilic attack of amine 2 on S 8 to produce the polysulfide A.M eanwhile, 1a reacts with N-methylpiperidine to give 1-benzyl-N-methylpiperidiniumc hloride B.…”

Section: Resultsmentioning

confidence: 99%

S₈‐Mediated One‐Pot Synthesis of Thioamides from Benzyl Chlorides and Amines

Pan

et al. 2016

Asian J Org Chem

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As traightforward and convenient method for the one-pot synthesis of thioamides has been developed by using at hree-component reaction involving readily available benzyl chlorides, amines, and elemental sulfur.Avarietyo f thioamidesw ere synthesized in satisfactory yields (up to 88 %). This approach was scalable and tolerated aw ide range of functional groups on the aromatic ring. It was also compatible with some heterocycle substrates, provided efficient and practical access to thioamides. No transition metals or externalo xidants were required in the reaction. A plausible mechanism is also proposed on the basis of some controlexperiments.Scheme1.Different routes for the synthesis of thioamides.[a] X. (P.R.C hina) Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under http://dx.

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Recent advances in the Willgerodt–Kindler reaction

Cited by 151 publications

References 89 publications

Sulfur Chemistry in Polymer and Materials Science

Sulfur Chemistry in Polymer and Materials Science

Palladium-catalyzed Suzuki-Miyaura coupling of thioureas or thioamides

S₈‐Mediated One‐Pot Synthesis of Thioamides from Benzyl Chlorides and Amines

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Recent advances in the Willgerodt–Kindler reaction

Cited by 151 publications

References 89 publications

Sulfur Chemistry in Polymer and Materials Science

Sulfur Chemistry in Polymer and Materials Science

Palladium-catalyzed Suzuki-Miyaura coupling of thioureas or thioamides

S8‐Mediated One‐Pot Synthesis of Thioamides from Benzyl Chlorides and Amines

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S₈‐Mediated One‐Pot Synthesis of Thioamides from Benzyl Chlorides and Amines