Silver‐Catalyzed Enantioselective Sulfimidation Mediated by Hydrogen Bonding Interactions

Reddy, Annapureddy Rajasekar; Burg, Finn; Gramüller, Johannes; Golub, Tino P.; Merten, Christian; Huber, Stefan M.; Bach, Thorsten

doi:10.1002/anie.202016561

Cited by 25 publications

(9 citation statements)

References 84 publications

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“…The routineness of the silver in the triad is obvious due to its relatively less relativistic effects than gold. Although the conventional hydrogen bonding interactions in transition metal complexes are well explored in general, however, the C–H···M interactions are much less explored in the coinage metal group in particular. − Although there are few examples of C–H···Au and C–H···Cu interactions in the literature, − the examples related to C–H···Ag are almost nonexistent. ,,, The present study offers a rare example of intermolecular C–H···Ag interactions between neighboring tetra(thiocyanato)corrolato-Ag(III) molecules in the crystal lattice. We have performed detailed theoretical investigations to support the experimentally obtained X-ray diffraction analysis.…”

Section: Introductionmentioning

confidence: 83%

Investigation of the Nature of Intermolecular Interactions in Tetra(thiocyanato)corrolato-Ag(III) Complexes: Agostic or Hydrogen Bonded?

et al. 2022

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Tetra(thiocyanato)corrolato-Ag(III) complexes presented here constitute a new class of metallo-corrole complexes. The spectroscopic properties of these complexes are quite unusual and interesting. For example, the absorption spectra of these β-substituted corrolato-Ag(III) complexes are very different from those of the β-unsubstituted corrolato-Ag(III) derivatives. Single-crystal XRD analysis of a representative tetra(thiocyanato)corrolato-Ag(III) derivative reveals C–H···Ag interactions. The C–H···Ag interactions are rarely demonstrated in the crystal lattice of a discrete coordination/organometallic compound. Optimization of the hydrogen positions of the crystal structure discloses the geometrical parameters of the said interaction as a Ag···H distance of 2.597 Å and ∠C–H···Ag of 109.62°. The natural bond orbital analysis provides information about the donor–acceptor orbitals involved in the interactions and their interaction energies. It was observed that the σC–H orbital overlaps with the vacant d-orbital of Ag with an interaction energy of 17.93 kJ/mol. The filled d-orbital of Ag overlaps with the σ*C–H orbital with an interaction energy of 4.79 kJ/mol. The highlights of this work are that the H···Ag distance is outside of the distance range for the typical agostic interaction but fitted with the weak H-bond distance. However, the ∠C-H···Ag angle is within the range of the agostic interaction. Both crystallographic data and electronic structure calculations reveal that these kinds of intermolecular interactions in square-planar d8 Ag(III) complexes are intermediate in nature. Thus, they cannot be categorically called either hydrogen bonding or agostic interaction.

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Section: Introductionmentioning

confidence: 83%

Investigation of the Nature of Intermolecular Interactions in Tetra(thiocyanato)corrolato-Ag(III) Complexes: Agostic or Hydrogen Bonded?

et al. 2022

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“…Nitrene-mediated S -imidation reactions of sulfides and sulfoxides with various nitrene precursors such as N -haloamides, oxaziridines, 1,4,2-dioxazol-5-ones, azides, and iminoiodinane derivatives under both metal-free and metal-catalyzed conditions have been well studied 51 – 61 . A variety of metal catalysts including iron, copper, rhodium, ruthenium, silver, and manganese-based complexes have been successfully employed in these transformations 54 – 56 .…”

Section: Resultsmentioning

confidence: 99%

Synthesis of N-acyl sulfenamides via copper catalysis and their use as S-sulfenylating reagents of thiols

Bai

Zhu

et al. 2022

Nat Commun

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Sulfur–heteroatom bonds such as S–S and S–N are found in a variety of natural products and often play important roles in biological processes. Despite their widespread applications, the synthesis of sulfenamides, which feature S–N bonds that may be cleaved under mild conditions, remains underdeveloped. Here, we report a method for synthesis of N-acyl sulfenamides via copper-catalyzed nitrene-mediated S-amidation reaction of thiols with dioxazolones. This method is efficient, convenient, and broadly applicable. Moreover, the resulting N-acetyl sulfenamides are highly effective S-sulfenylation reagents for the synthesis of unsymmetrical disulfides under mild conditions. The S-sulfenylation protocol enables facile access to sterically demanding disulfides that are difficult to synthesize by other means.

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“…[7,8] While the synthesis of racemic sulfilimines has been well-developed, asymmetric methodologies remain less common. To date, only a few stereoselective methods with Ag, [9] Co, [10] Cu, [11,12] Ru, [13 -15] Mn, [16,17] Rh [18] and Fe [19] catalysts have been reported. These methods are generally effective, but often rely on complex catalytic systems or hazardous reagents.…”

Section: Introductionmentioning

confidence: 99%

Advances in Stereoselective Iron(II)‐Catalyzed Synthesis of Sulfilimines with N‐Mesyloxycarbamates

Lebel

Lai

2021

Helvetica Chimica Acta

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A stereoselective amination of thioethers to access sulfilimines using N-mesyloxycarbamates in a catalytic system composed of iron chloride (II) and a pyridine oxazoline (PyOX) ligand, has been developed. The reaction proceeds with modest to good yields and selectivities (up to 86 : 14 d.r. and 72 : 28 e.r.). Selectivity was controlled by both the structure of the chiral ligand and the amination reagent.

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Silver‐Catalyzed Enantioselective Sulfimidation Mediated by Hydrogen Bonding Interactions

Cited by 25 publications

References 84 publications

Investigation of the Nature of Intermolecular Interactions in Tetra(thiocyanato)corrolato-Ag(III) Complexes: Agostic or Hydrogen Bonded?

Investigation of the Nature of Intermolecular Interactions in Tetra(thiocyanato)corrolato-Ag(III) Complexes: Agostic or Hydrogen Bonded?

Synthesis of N-acyl sulfenamides via copper catalysis and their use as S-sulfenylating reagents of thiols

Advances in Stereoselective Iron(II)‐Catalyzed Synthesis of Sulfilimines with N‐Mesyloxycarbamates

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