“…Note also that the oxidation of COSS in the presence of H 2 O 2 , peracetic acid or dimethyloxirane , selectively affords the 1-oxide (or the 1,1-dioxide known as the Beaucage reagent). , 3 H -1,2-Benzothiaselenol-3-one ( COSeS ) is also known as an efficient reagent for stereospecific selenization of H -phosphates and H -phosphonothioate diesters to afford Se-derivatized RNAs, DNAs and proteins, , an important issue to overcome the problems faced in their X-ray crystallographic studies . It is also reported as a potent fungicide at 1 ppm and shows herbicidal and insecticidal activity at higher concentrations .…”
Section: Introductionmentioning
confidence: 99%
“…In the thiocarbonyl series, X-ray crystal structures have been reported for the three CSSS , CSSSe , and CSSeS derivatives ( CSSeSe is unknown). The 1,2-dithiole derivative CSSS exhibits a reactivity comparable to COSS , with ring opening between the CS and S–S moieties, by sp 2 nitrogen nucleophiles or by active methylene compounds, or with selective oxidation by H 2 O 2 into the 1-oxide …”
Section: Introductionmentioning
confidence: 99%
“…The 1,2-dithiole derivative CSSS exhibits a reactivity comparable to COSS, with ring opening between the CS and S−S moieties, by sp 2 nitrogen nucleophiles 28 or by active methylene compounds, 29 or with selective oxidation by H 2 O 2 into the 1-oxide. 17 The work described here aims at rationalizing both the specific reactivity and the molecular assembly in the solid-state structures of these series of compounds, as models for many others involving a disulfide or diselenide bond. For that purpose, we have synthesized six of these eight derivatives.…”
Molecular assembly and reactivity have been investigated with a series of 3H-1,2-benzodithiol-3-(thi)one derivatives and their (mixed) selenated analogs. Electrostatic potential calculations on monomers show three σ-hole regions around the dichalcogenide Ch−Ch bond (Ch = S, Se), one side-on and two along the bonding direction. The topological analysis of the electron density ρ(r) points the weak nature of the Ch−Ch bond. σ-hole and lone-pair regions are described in terms of charge depletion (CD) and charge concentration (CC) sites found in the valence shell of chalcogen atoms. Whereas CD and CC sites are characterized by the topological critical points of L(r) = −∇ 2 ρ(r), their electrophilic and nucleophilic power are measured by the corresponding L/ρ magnitudes. In crystal structures, each chalcogen bond (ChB) involves a σ-hole region and shows a CD⋅⋅⋅CC interaction that aligns with the internuclear direction of the atoms the CD and CC sites belong. The alignment holds simultaneously for all of the ChB interactions in each crystal structure, indicating that CD⋅⋅⋅CC interactions drive molecular orientation in molecular assembly. Strength of ChB is measured in terms of the topological properties of ρ(r), whereas the intensity of the electrophilic…nucleophilic interaction is monitored by [(L/ρ)CC -(L/ρ)CD]/d 2 CC…CD. The σhole in side-on conformation forms the strongest ChB interactions in molecular assembly. Reactivity of molecules against nucleophilic attack has been investigated along each of the three σ-hole regions by using fluoride as a probe. Adducts formed along the Ch−Ch bonding direction are energetically more favorable than in side-on conformation. At optimized geometries, the
“…Note also that the oxidation of COSS in the presence of H 2 O 2 , peracetic acid or dimethyloxirane , selectively affords the 1-oxide (or the 1,1-dioxide known as the Beaucage reagent). , 3 H -1,2-Benzothiaselenol-3-one ( COSeS ) is also known as an efficient reagent for stereospecific selenization of H -phosphates and H -phosphonothioate diesters to afford Se-derivatized RNAs, DNAs and proteins, , an important issue to overcome the problems faced in their X-ray crystallographic studies . It is also reported as a potent fungicide at 1 ppm and shows herbicidal and insecticidal activity at higher concentrations .…”
Section: Introductionmentioning
confidence: 99%
“…In the thiocarbonyl series, X-ray crystal structures have been reported for the three CSSS , CSSSe , and CSSeS derivatives ( CSSeSe is unknown). The 1,2-dithiole derivative CSSS exhibits a reactivity comparable to COSS , with ring opening between the CS and S–S moieties, by sp 2 nitrogen nucleophiles or by active methylene compounds, or with selective oxidation by H 2 O 2 into the 1-oxide …”
Section: Introductionmentioning
confidence: 99%
“…The 1,2-dithiole derivative CSSS exhibits a reactivity comparable to COSS, with ring opening between the CS and S−S moieties, by sp 2 nitrogen nucleophiles 28 or by active methylene compounds, 29 or with selective oxidation by H 2 O 2 into the 1-oxide. 17 The work described here aims at rationalizing both the specific reactivity and the molecular assembly in the solid-state structures of these series of compounds, as models for many others involving a disulfide or diselenide bond. For that purpose, we have synthesized six of these eight derivatives.…”
Molecular assembly and reactivity have been investigated with a series of 3H-1,2-benzodithiol-3-(thi)one derivatives and their (mixed) selenated analogs. Electrostatic potential calculations on monomers show three σ-hole regions around the dichalcogenide Ch−Ch bond (Ch = S, Se), one side-on and two along the bonding direction. The topological analysis of the electron density ρ(r) points the weak nature of the Ch−Ch bond. σ-hole and lone-pair regions are described in terms of charge depletion (CD) and charge concentration (CC) sites found in the valence shell of chalcogen atoms. Whereas CD and CC sites are characterized by the topological critical points of L(r) = −∇ 2 ρ(r), their electrophilic and nucleophilic power are measured by the corresponding L/ρ magnitudes. In crystal structures, each chalcogen bond (ChB) involves a σ-hole region and shows a CD⋅⋅⋅CC interaction that aligns with the internuclear direction of the atoms the CD and CC sites belong. The alignment holds simultaneously for all of the ChB interactions in each crystal structure, indicating that CD⋅⋅⋅CC interactions drive molecular orientation in molecular assembly. Strength of ChB is measured in terms of the topological properties of ρ(r), whereas the intensity of the electrophilic…nucleophilic interaction is monitored by [(L/ρ)CC -(L/ρ)CD]/d 2 CC…CD. The σhole in side-on conformation forms the strongest ChB interactions in molecular assembly. Reactivity of molecules against nucleophilic attack has been investigated along each of the three σ-hole regions by using fluoride as a probe. Adducts formed along the Ch−Ch bonding direction are energetically more favorable than in side-on conformation. At optimized geometries, the
“…However, the problem appears to be more complicated since Gates et al have discovered an additional way for the alkylative DNA cleavage of leinamycin that is independent of thiols, and water serves as the trigger. Although the DNA splitting of several simple 1,2-dithiolan-3-one- S -oxides have been demonstrated, only one report deals with their biological activity, and the investigated compounds were found to be slightly cytostatic or were inactive. 1 DNA Cleavage Mechanism of Leinamycin…”
A simple synthesis of 1,2-dithiolan-3-ones from alpha,beta-unsaturated thiophenyl esters is reported. Introduction of the biologically active 1,2-dithiolan-3-one-1-oxide moiety of leinamycin into aldehydo-d-arabinose 11, the uridine derivative 16, and the deoxythymidine 21 was established. An extended bioactive part of leinamycin carrying a carbon-carbon triple bond was also synthesized. All of these analogues of leinamycin showed cytotoxic activity against HeLa3 tumor cells. Interestingly, the lipophilic, silyl group-containing derivatives proved to be more active than the hydrophilic counterparts.
“…1,2-Benzodithiol-3-ones and derivatives thereof have demonstrated prominent biological activities including antitumor, antioxidant, and COX/5-LOX inhibition activity, − which could also be widely utilized to prepare fluorescent probes . In addition, 1,2-benzodithiol-3-ones are the precursors to engender 3 H -1,2-benzodithiol-3-one 1-oxides, which are eminent thiol-activated DNA-cleaving agents .…”
An expedient synthesis of benzo [c][1,2]dithiol-3ones via metal-free denitrogenative transannulation of benzotriazinones is developed, which represents the first example of acidmediated heteroannulation of benzotriazinones. This newly discovered reactivity of benzotriazinones enables the streamline synthesis of diverse benzo[c][1,2]dithiol-3-ones in decent yields by using sodium sulfide as the sulfur source under simple reaction conditions.
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