Sulfur Groups Improve the Performance of Triazole- and Triazolium-Based Interaction Units in Anion Binding

Álvarez-Pérez, Mónica; Velado, Marina; García-Puentes, Diego; Sáez, Estéban; Vicent, Cristina; Pradilla, Roberto Fernández de la; Viso, Alma; Torre, Marı́a C. de la; Sierra, Miguel Á.

doi:10.1021/acs.joc.7b00261

Cited by 5 publications

(7 citation statements)

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“…The results presented above show the potential of MICs derived from 1,2,3-triazoles having a chiral sulfur functional group at the C5 position. While for some applications like anion recognition the effect of the sulfur groups is to decrease the electronic density of the triazole ring, 23 the participation of these groups in determining the nature and stereochemistry of the final product is decisive. In catalytic cycloisomerization processes and cycloisomerization−dimerization processes, the role of the sulfoxide moiety is to stabilize intermediates in the catalytic cycle, allowing for the reaction to occur or significantly increasing the selectivity of the cyclization processes.…”

Section: Discussionmentioning

confidence: 99%

“…The subsequent transformation of triazoles 12 into sulfoximines 15 (route d in Scheme 5) was affected by the chemoselective oxidation with m -CPBA to form the corresponding sulfonyl triazole 14 and subsequent imination 22 with PhI=NTs/Cu(OTf) 2 to form the racemic sulfoximine 15 in an excellent yield (a in Scheme 8). 23 Enantiopure sulfoximines 15 were prepared avoiding the oxidation step by the reaction of triazole sulfoxides 12 and PhI=NTs/Cu(OTf) 2 . Subsequent methylation yielded the enantiopure salts 16 (b in Scheme 8).…”

Section: Synthesismentioning

confidence: 99%

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1,2,3-Triazolium-Derived Mesoionic Carbene Ligands Bearing Chiral Sulfur-Based Moieties: Synthesis, Catalytic Properties, and Their Role in Chirality Transfer

Sierra

Torre

2019

ACS Omega

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1,2,3-Triazole-derived mesoionic carbenes (MICs) having a chiral sulfur functional group at the C5 position are easily available through a CuAAC between chiral alkynyl sulfoxides and different azides. The MICs form complexes with several metals (Au, Ag, Ir, Rh, and Ru) that are enantiomerically pure. Moreover, enantiomerically pure MIC sulfinilimines are obtained from the corresponding sulfoxide retaining the chirality. Through this article, the participation of sulfoxide moieties in different catalytic and chirality transfer processes, as well as in discovering mechanistically new processes will be shown. The role of the sulfur chiral moiety in catalytic cycloisomerization and cycloisomerization–dimerization processes using Au–MIC catalysts is dual. The sulfur functional group either stabilizes intermediates in the catalytic cycle, allowing for the reaction to occur or significantly increases the selectivity of the cyclization processes. 1,2,3-Triazole MICs having chiral sulfoxides at C5 are extremely efficient in preparing chiral at the metal complexes by C–H insertion processes. The chiral at the metal half-sandwich complexes, having the enantiopure sulfur chiral group unaltered, experiences different reactions with complete retention of the configuration. Finally, mechanistically new processes, like the desulfinilation of 1,2,3-triazolium salts in Ag–MIC complexes have been uncovered. These still-nascent classes of compounds will offer opportunities for the discovery of novel catalytic applications and to study new mechanistically sound processes.

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Section: Discussionmentioning

confidence: 99%

Section: Synthesismentioning

confidence: 99%

1,2,3-Triazolium-Derived Mesoionic Carbene Ligands Bearing Chiral Sulfur-Based Moieties: Synthesis, Catalytic Properties, and Their Role in Chirality Transfer

Sierra

Torre

2019

ACS Omega

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“…[16,75] 4-Sulfinyl-1,2,3triazoles, which were prepared by CuAAC, displayed fluorescence and anion binding performance. [76][77]…”

Section: -Sulfanyl-123-triazoles and 4-sulfinyl-123-triazolesmentioning

confidence: 99%

“…The chiral sulfoxides and sulfoximines opened the feasibility of further application of these recognition units in donor acceptor-accept-or donor (DA-AD) recognition or enantio-discrimination of chiral anions (Scheme 7). [77] Scheme 6. Synthesis of 1,2,3-triazoles Ir(III) coordination compounds.…”

Section: -Sulfinyl-123-triazolesmentioning

confidence: 99%

Sulfur‐Containing 1,2,3‐Triazoles: Synthesis and Properties

Peng,

Chen,

Chen

et al. 2024

Eur J Org Chem

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Sulfur‐containing 1,2,3‐triazoles display bioactivities like antidepressant, antifungal activity, antitumor, etc. Numerous approaches have been established to form sulfur‐containing 1,2,3‐triazoles. 4‐Sulfanyl‐ and 5‐ sulfanyl‐1,2,3‐triazoles were produced by metal‐catalyzed azide‐alkyne cycloaddition (AAC), etc. N‐Sulfonyl‐1,2,3‐triazoles were generated via the reaction of acetylides with sulfonyl azides, CuAAC. 4‐Sulfonyl‐1,2,3‐triazoles were produced through [3+2] cycloaddition and reaction of azide with bromovinylsulfonyl fluoride. Although 5‐sulfonyl‐1,2,3‐triazoles were formed successfully via RuAAC, their synthetic approaches were very limited. 1‐Phosphinyl‐2‐sulfanylethynes were suitable substances to access sulfur‐ and phosphorus‐containing triazoles. In this review, the synthesis and properties of sulfur‐containing 1,2,3‐triazoles were highlighted. Initially, the properties of organosulfurs, 1,2,3‐triazoles and sulfur‐containing 1,2,3‐triazoles were briefly introduced. After stating the general procedures to construct 1,2,3‐triazole skeleton, the synthetic approaches and properties of sulfur‐involved 1,2,3‐triazoles were sorted and described in details. According to different kinds of sulfur‐containing 1,2,3‐triazoles, synthetic methods and features of 4‐sulfanyl‐1,2,3‐triazoles, 5‐sulfanyl‐1,2,3‐triazoles, N‐sulfonyl‐1,2,3‐triazoles, 4‐sulfonyl‐1,2,3‐triazoles, 5‐sulfonyl‐1,2,3‐triazoles, sulfur‐ and heteroatom‐containing 1,2,3‐triazoles were summarized.

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“…2 Merging thioether with triazole in the same molecule is, in principle, an efficient strategy to combine the advances of these two fragments and could result in unprecedented molecular properties. 3 For instance, the thioether-containing bioisosteric triazole analogues of RN-18 represent a new class of potent Vif antagonists as preclinical candidates for novel AIDS therapy. 3 a Phosphorus-thioether hybrid ligands containing triazole moieties have been widely employed in many asymmetric transformations (Scheme 1a).…”

mentioning

confidence: 99%

Iridium-catalysed thioether-directed regioselective cycloaddition of internal alkynes with azides

et al. 2023

Org. Biomol. Chem.

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Sulfur Groups Improve the Performance of Triazole- and Triazolium-Based Interaction Units in Anion Binding

Cited by 5 publications

References 50 publications

1,2,3-Triazolium-Derived Mesoionic Carbene Ligands Bearing Chiral Sulfur-Based Moieties: Synthesis, Catalytic Properties, and Their Role in Chirality Transfer

1,2,3-Triazolium-Derived Mesoionic Carbene Ligands Bearing Chiral Sulfur-Based Moieties: Synthesis, Catalytic Properties, and Their Role in Chirality Transfer

Sulfur‐Containing 1,2,3‐Triazoles: Synthesis and Properties

Iridium-catalysed thioether-directed regioselective cycloaddition of internal alkynes with azides

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