Sulfoxides and Sulfilimines

Ōae, Shigeru

doi:10.1007/978-1-4684-2049-4_8

Cited by 27 publications

(13 citation statements)

References 424 publications

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“…For L = NH 2 the alkylated sulfoxide isomerizes to the O-bound product, while for L = COO - , “oxygen loss” (presumably via production of formaldehyde) occurs yielding a metallothiolate, which is subsequently alkylated . This mechanism is based on the well-studied DMSO-promoted oxidation reactions . A similar mechanism is proposed for the methylation of Ni-5* and Ni-6* .…”

Section: Resultsmentioning

confidence: 83%

Alkylation-Induced O-Atom Rearrangement in Nickel S-Oxygenates

et al. 1998

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Reactions of organic halides MeI and Br(CH2)3Br with square planar nickel complexes of tetradentate N2SS‘ or N2S‘2 ligands (S‘ = RS(O)) have been explored for their potential to direct alkylation of metallosulfoxide sulfur and yield metal-bound organic sulfoxides. In fact, as established by spectroscopic and electrochemical signatures, isolated products were characterized as the result of O-atom rearrangements or transfers leading primarily to metallosulfones (Ni−SO2R) and metallothiolates (Ni−SR) (which were subsequently alkylated to nickel-bound thioethers). Proposed intermediates in the reactions of the monosulfoxide, Ni-4*, N-(2-mercapto-2-(methylpropyl))-N‘-(2-sulfenato-2-(methylpropyl))-1,5-diazacyclooctanenickel(II) and the bis-sulfoxide, Ni-5*, N,N‘-bis(2-sulfenato-2-(methylpropyl))-1,5-diazacyclooctanenickel(II), with 1,3-dibromopropane include S-bound R‘S−OR moieties resulting from ring closure of the pendant alkyl bromide on the nucleophilic sulfoxide oxygen. X-ray crystal structures of N-(sulfinato-2-(methylpropyl))-N‘-(2-thia-2-(methylpropyl))-1,5-diazacyclooctanenickel(II) iodide and a bimetallic composed of two units of N-(2-mercapto-2-(methylpropyl))-N‘-(2-sulfinato-2-(methylpropyl))-1,5-diazacyclooctanenickel(II) linked by (CH2CH2CH2) are reported.

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Section: Resultsmentioning

confidence: 83%

Alkylation-Induced O-Atom Rearrangement in Nickel S-Oxygenates

et al. 1998

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“…Sulfilimines―mono-aza analogues of sulfoxides―were first reported in 1921 . The S–N bond in sulfilimines is more reactive and polarized than the S–O bond in sulfoxides (Figure a) . Due to the interesting features of this moiety, sulfilimines have played important roles in a broad range of fields, including synthetic chemistry, catalysis, crop protection, and medicinal chemistry .…”

Section: Introductionmentioning

confidence: 99%

“…In general, the nitrogen end of the sulfilimine linkage is stabilized by strong electron-withdrawing groups (Figure a) . Among the possible diversity of the imine nitrogen, we are particularly interested in the cyano substituent, which exhibits high metabolic stability, a powerful electron-withdrawing nature, and improved ADME-toxicology profiles …”

Section: Introductionmentioning

confidence: 99%

Selective Synthesis of N-Cyano Sulfilimines by Dearomatizing Stable Thionium Ions

et al. 2020

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For the selective synthesis of N-cyano sulfilimines, we have developed a new method based on the soft−soft interaction between thionium ion electrophiles and cyanonitrene nucleophiles. The stable thionium ion was successfully obtained by oxidative dearomatization using phenyliodine (III) diacetate (PIDA) in N,N-dimethylformamide (DMF). The sulfur imination reactions were tolerant to a wide range of functional groups and exhibited high selectivities and excellent yields. The existence of thionium ion intermediates was confirmed by ultraviolet/visible (UV/vis) spectroscopy and 1 H NMR experiments.

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“…Among sulfur-containing ylides, whereas sulfonium ylides have been widely studied, sulfilimines are less explored. This readily available ylidic unit can serve as valuable synthetic intermediates through a cleavage of the polarized N–S bond .…”

mentioning

confidence: 99%

N-Pyridinyl Sulfilimines as a Source for α-Imino Gold Carbenes: Access to 2-Amino-Substituted N-Fused Imidazoles

et al. 2019

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Gold-catalyzed formal 1,3-dipolar annulation between readily accessible N-pyridinylsulfilimines and ynamides is reported. A diverse set of imidazole derivatives is prepared from the corresponding sulfilimines and ynamides. These functionalized cyclic products can undergo further transformations to afford diverse imidazole frameworks. Moreover, in situ synthesis is feasible and shows good potential in the synthesis of nucleoside analogues.

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Sulfoxides and Sulfilimines

Cited by 27 publications

References 424 publications

Alkylation-Induced O-Atom Rearrangement in Nickel S-Oxygenates

Alkylation-Induced O-Atom Rearrangement in Nickel S-Oxygenates

Selective Synthesis of N-Cyano Sulfilimines by Dearomatizing Stable Thionium Ions

N-Pyridinyl Sulfilimines as a Source for α-Imino Gold Carbenes: Access to 2-Amino-Substituted N-Fused Imidazoles

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