Regio- and Stereospecific Synthesis of β-Sulfonamidodisulfides and β-Sulfonamidosulfides from Aziridines using Tetrathiomolybdate as a Sulfur Transfer Reagent

Sureshkumar, Devarajulu; Gunasundari, Thanikachalam; Ganesh, Venkataraman; Chandrasekaran, Srinivasan

doi:10.1021/jo0624389

Cited by 42 publications

(26 citation statements)

References 30 publications

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“…We also note that while the Sharpless aziridination is reported to take 12 hours at room temperature [26,27], the reaction of compound 1 went to completion within 40 minutes at 0 °C. The reaction gave similar results whether run at room temperature or at 0 °C.…”

Section: Methodsmentioning

confidence: 70%

“…Similarly, reaction with NBS, ethanol, and pyridine showed a mixture that appeared to contain one ethoxy group. Scheme 6 [27] Attempts were also made to put on acetate groups by reaction of compound 1 with NBS and acetate ion [23]. Sodium acetate in acetic acid gave very little product of any sort, as did sodium acetate in water.…”

Section: -Carene and Oxygen Nucleophilesmentioning

confidence: 99%

“…One of the better general methods for accomplishing the aziridination of alkenes is Sharpless' reaction, in which a source of Br + (phenyltrimethylammonium tribromide, PTAB) catalyses a process using chloramine-T (TsNNaCl) as the nitrogen source [26]. The reaction is believed to proceed through a bromonium ion [26], and has been successfully used by Chandrasekaran for the preparation of tosyl aziridine 6 of (+)-3-carene 3 (Scheme 6) [27]. The intermediate bromonium ion in that case was not adjacent to the cyclopropane ring, and the cyclopropane ring remained unaffected [27].…”

Section: -Carene and Nitrogen Nucleophilesmentioning

confidence: 99%

“…The reaction is believed to proceed through a bromonium ion [26], and has been successfully used by Chandrasekaran for the preparation of tosyl aziridine 6 of (+)-3-carene 3 (Scheme 6) [27]. The intermediate bromonium ion in that case was not adjacent to the cyclopropane ring, and the cyclopropane ring remained unaffected [27].…”

Section: -Carene and Nitrogen Nucleophilesmentioning

confidence: 99%

“…We performed the reaction of compound 1 according to the procedure of Sharpless [26,27]. The major product 13 was a solid.…”

Section: -Carene and Nitrogen Nucleophilesmentioning

confidence: 99%

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Reactions of the halonium ions of carenes and pinenes: An experimental and theoretical study

et al. 2015

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The reactions of vinylcyclopropane (+)-2-carene (1) and vinylcyclobutanes (-)-β-pinene (7), (-)-α-pinene (11), and (-)-nopol (12) with electrophilic halogens in the presence of oxygen and nitrogen nucleophiles in various solvents have been investigated. The halonium ion intermediates that were presumably formed were very reactive and led to opening of the conjugated cyclopropane or cyclobutane. Reactions of chloramine-T trihydrate with compound 1 in acetonitrile gave amidine 13 and diazepine 14. Reactions of chloramine-T trihydrate with pinenes in methylene chloride gave allylic tosylamines 22, 16B and 24. Mechanisms to explain the observations are proposed and supported by ab initio and Density Functional Theory calculations on the carenes and pinenes in this report and their bromonium ion intermediates. For comparisons, the relative extent of conjugation with the bromonium ion moiety of these, as well as select cyclohexene and cyclohexadiene systems and their corresponding bromonium ions, were optimized at the B3LYP/cc-pVDZ level of theory, and then these geometries were analyzed using the absolute hardness index at the HartreeFock/aug-cc-pVDZ and B3LYP/aug-cc-pVDZ levels of theory. Additionally, Natural Population Analysis charges were calculated for these systems using Møller-Plessett Second-Order Perturbation Theory electron densities and the aug-cc-pVDZ basis set. Combining the results of these theoretical methods with analysis of structural details of their optimized geometries gives much electronic structure insight into the extent of conjugation of bromonium ions of the carenes and pinenes reported here, and places them in relative context of more traditional conjugated and non-conjugated bromonium ion systems. In particular, bromonium ions of compounds 1, 7, and 11 display structural distortions, charge delocalizations and hardness values comparable with those of traditional conjugated cyclohexadienes, with possible reasons for subtle differences presented.

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Section: Methodsmentioning

confidence: 70%

Section: -Carene and Oxygen Nucleophilesmentioning

confidence: 99%

Section: -Carene and Nitrogen Nucleophilesmentioning

confidence: 99%

Section: -Carene and Nitrogen Nucleophilesmentioning

confidence: 99%

“…We performed the reaction of compound 1 according to the procedure of Sharpless [26,27]. The major product 13 was a solid.…”

Section: -Carene and Nitrogen Nucleophilesmentioning

confidence: 99%

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Reactions of the halonium ions of carenes and pinenes: An experimental and theoretical study

et al. 2015

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Domino Reactions Initiated by Nucleophilic Substitution

2013

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Step‐growth Polymerization of Aziridines with Elemental Sulfur: Easy Access to Linear Polysulfides and Their Use as Recyclable Adhesives

Huang,

Zheng,

Luo

et al. 2024

Angewandte Chemie

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The bulk radical polymerization of bis(aziridine) with molten elemental sulfur resulted in brittle, cross‐linked polymers. However, when the bis(aziridine) was treated with elemental sulfur in the presence of an organobase, the ring‐opening reaction of aziridine with oligosulfide anions occurred, leading to the formation of linear polymers by step‐growth polymerization. These newly synthesized polymers possess repeating units containing a sulfonamide or amide functional moiety and oligosulfide bonds with an average sulfur segment of about two. A small molecular model reaction confirmed the nucleophilic addition reaction of elemental sulfur to aziridine. It was verified that S–S dynamic bond exchange takes place in the presence of an organic base within the linear chains. The mixture of the synthesized polysulfides with pyridine exhibits exceptional adhesive properties when applied to steel, and aluminum substrates. Notably, these prepared adhesives displayed good reusability due to the dynamic S‐S exchange and complete recyclability due to their solution processability. This elemental sulfur‐involved polymerization approach represents an innovative method for the synthesis of advanced sulfur‐containing polymers, demonstrating the potential for various applications in adhesives and beyond.

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Regio- and Stereospecific Synthesis of β-Sulfonamidodisulfides and β-Sulfonamidosulfides from Aziridines using Tetrathiomolybdate as a Sulfur Transfer Reagent

Cited by 42 publications

References 30 publications

Reactions of the halonium ions of carenes and pinenes: An experimental and theoretical study

Reactions of the halonium ions of carenes and pinenes: An experimental and theoretical study

Domino Reactions Initiated by Nucleophilic Substitution

Step‐growth Polymerization of Aziridines with Elemental Sulfur: Easy Access to Linear Polysulfides and Their Use as Recyclable Adhesives

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