Catalyst‐Free Regio‐ and Stereospecific Synthesis of β‐Sulfonamido Dithiocarbamates: Efficient Ring‐Opening Reactions of <i>N</i>‐Tosyl Aziridines by Dialkyldithiocarbamates

Alagiri, Kaliyamoorthy; Prabhu, Kandikere Ramaiah

doi:10.1002/chem.201100817

Cited by 21 publications

(8 citation statements)

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“…They are also nucleophilic enough to attack epoxides and aziridines resulting in ring-opening (eq. 11) both of which are synthetically useful [17]. …”

Section: General Chemistrymentioning

confidence: 99%

Metal-dithiocarbamate complexes: chemistry and biological activity

Hogarth¹

2012

MRMC

255

157

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Dithiocarbamates are highly versatile mono-anionic chelating ligands which form stable complexes with all the transition elements and also the majority of main group, lanthanide and actinide elements. They are easily prepared from primary or secondary amines and depending upon the nature of the cation can show good solubility in water or organic solvents. They are related to the thiuram disulfides by a one-electron redox process (followed by dimerisation via sulfur-sulfur bond formation) which is easily carried out upon addition of iodide or ferric salts. Dithiocarbamates are lipophilic and generally bind to metals in a symmetrical chelate fashion but examples of other coordination modes are known, the monodentate and anisobidentate modes being most prevalent. They are planar sterically non-demanding ligands which can be electronically tuned by judicious choice of substituents. They stabilize metals in a wide range of oxidation states, this being attributed to the existence of soft dithiocarbamate and hard thioureide resonance forms, the latter formally resulting from delocalization of the nitrogen lone pair onto the sulfurs, and consequently their complexes tend to have a rich electrochemistry. Tetraethyl thiuramdisulfide (disulfiram or antabuse) has been used as a drug since the 1950s but it is only recently that dithiocarbamate complexes have been explored within the medicinal domain. Over the past two decades anti-cancer activity has been noted for gold and copper complexes, technetium and copper complexes have been used in PET-imaging, dithiocarbamates have been used to treat acute cadmium poisoning and copper complexes also have been investigated as SOD inhibitors.

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“…They are also nucleophilic enough to attack epoxides and aziridines resulting in ring-opening (eq. 11) both of which are synthetically useful [17]. …”

Section: General Chemistrymentioning

confidence: 99%

Metal-dithiocarbamate complexes: chemistry and biological activity

Hogarth¹

2012

MRMC

255

157

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“…A); (ii) the reaction of alkyl halides and tetramethylthiuram disulfides, which are commonly prepared by the oxidative coupling of dialkylcarbamodithioic acid salts (Scheme , eq. B); (iii) the reaction of amines with expensive and toxic reagents, such as thiophosgene or isothiocyanate; and (iv) ring‐opening reactions of epoxides and N ‐tosyl aziridines with dialkylcarbamodithioic acid salts (Scheme , eq. C).…”

Section: Methodsmentioning

confidence: 99%

Copper‐Catalyzed C−S Coupling of Quaternary Ammonium Salts and Dialkylcarbamodithioic Acid Salts

et al. 2020

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An efficient synthesis of (chiral) alkyl dialkylcarbamodithioates via a CuI-catalyzed CÀ S cross-coupling reaction of (chiral) quaternary ammonium salts and (chiral) dialkylcarbamodithioic acid salts has been developed. CÀ S coupling products were obtained with extremely high ee values and yields, with enantioenriched arylmethyl trimethylammonium triflates affording the inverse absolute configuration.

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“…Many examples of the ring-opening of aziridines by various carbon [29–30], nitrogen [31–32], oxygen [33–34], sulfur [35–36] and halogen [37–39] nucleophilic reagents in the presence of catalytic amounts of small acids and bases such as BF 3 ·Et 2 O, AcOH, TsOH, TFA, PBu 3 , TMEDA, TBAF, Bu 4 NHSO 4 , pyridine N -oxide, and N -heterocyclic carbenes were published. However, the enantioselective ring-opening of meso -aziridines in the presence of chiral organocatalysts ( OC ) has emerged as a research field only in recent years.…”

Section: Reviewmentioning

confidence: 99%