Metal-free Reductive Deoxygenation of Sulfoxides by an Organosilicon Reductant, 1,1′-Bis(trimethylsilyl)-1<i>H</i>,1′<i>H</i>-4,4′-bipyridinylidene

Bhattacharjee, Argha; Hosoya, Hiromu; Yurino, Taiga; Tsurugi, Hayato; Mashima, Kazushi

doi:10.1246/cl.190340

Cited by 6 publications

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“…We have focused our attention on the versatility of a family of organosilicon-based reductants, 1,4-bis(trimethylsilyl)-1,4-dihydropyrazine derivatives and 1,1′-bis(trimethylsilyl)-4,4′-bipyridinylidene, as stoichiometric reagents for reducing not only transition metal complexes 10 for reductive C–C bond formation without generating any metal-based waste, 10 b ,10 d but also main group halides for producing multiple bonds between main group elements 11 and some oxo compounds, such as nitrobenzenes and sulfoxides, in a metal-free fashion to give respectively anilines and thioethers. 12 c ,12 d Herein, we report that chromium( iii ) trichloride with N , N , N ′, N ′-tetramethylethylenediamine (TMEDA) served as a catalyst for the cyclopropanation of alkenes with bromoform in combination with 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-dihydropyrazine ( 1a ) to obtain synthetically useful bromocyclopropanes in high yield ( Fig. 1c ).…”

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confidence: 99%

Chromium-catalyzed cyclopropanation of alkenes with bromoform in the presence of 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-dihydropyrazine

et al. 2020

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Section: Introductionmentioning

confidence: 99%

Chromium-catalyzed cyclopropanation of alkenes with bromoform in the presence of 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-dihydropyrazine

et al. 2020

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B₂cat₂‐Mediated Reduction of Sulfoxides to Sulfides

2020

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An efficient and operationally simple method for the reduction of sulfoxides to sulfides has been developed using bis(catecholato)diboron (B 2 cat 2 ) as a reducing agent. The present method accommodates various functional groups which are generally prone to reduction: halides, alkynes, Organosulfur compounds have occupied important positions as bioactive entities, functional materials, and useful building blocks or reagents in organic synthesis. [1] Among organosulfur compounds, sulfoxides have attracted attention of synthetic chemists because of the unique reactivity as is seen in Swern oxidation [2] and Pummerer-type reactions. [3] Besides these classical reactions, sulfoxides are also utilized in asymmetric transformations as chiral auxiliaries. [4] Moreover, owing to the coordination ability to transition metals, sulfoxides promote catalytic C-H functionalizations as directing groups. [5] After these reactions, the sulfoxide moiety can be removed, which often accompanies the reduction of sulfoxides to sulfides and subsequent desulfurization. From that perspective, reduction of sulfoxides to sulfides is a simple yet important process in organic synthesis. [6] Although there are many reports on reduction of sulfoxides by means of metal hydrides [7] or low-valent transition metals, [8] these reactions intrinsically suffer from competing reduction of other functionalities such as carbonyls. Sulfur(II) compounds [9] and phosphines [10] are also known to promote the reduction of sulfoxides, but they often encounter purification problems. In the former case, separation of the resulting sulfide products from the remaining sulfur(II) reductants such as thiols and sulfides can be problematic. The latter faces the formation of phosphine oxides as by-products that are tedious to remove. Efficient methods achieving good functional group tolerance and facile purification of the products are of high demand.Recently we have been interested in the development of reductive transformations using diboron reagents. [11] During our investigation, we found that sulfoxides were reduced to the corresponding sulfides by means of diborons. Although there are two reports on the reduction of sulfoxides with bis(pinacolato)diboron (B 2 pin 2 ) as a deoxygenating reagent, [12] catalysts, long [a]

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Reduction of S O and SO2 to S, S–X to S–H, and P O to P

Magné,

Serusi,

Gulea

et al. 2024

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Metal-free Reductive Deoxygenation of Sulfoxides by an Organosilicon Reductant, 1,1′-Bis(trimethylsilyl)-1H,1′H-4,4′-bipyridinylidene

Cited by 6 publications

References 42 publications

Chromium-catalyzed cyclopropanation of alkenes with bromoform in the presence of 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-dihydropyrazine

Chromium-catalyzed cyclopropanation of alkenes with bromoform in the presence of 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-dihydropyrazine

B₂cat₂‐Mediated Reduction of Sulfoxides to Sulfides

Reduction of S O and SO2 to S, S–X to S–H, and P O to P

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Metal-free Reductive Deoxygenation of Sulfoxides by an Organosilicon Reductant, 1,1′-Bis(trimethylsilyl)-1H,1′H-4,4′-bipyridinylidene

Cited by 6 publications

References 42 publications

Chromium-catalyzed cyclopropanation of alkenes with bromoform in the presence of 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-dihydropyrazine

Chromium-catalyzed cyclopropanation of alkenes with bromoform in the presence of 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-dihydropyrazine

B2cat2‐Mediated Reduction of Sulfoxides to Sulfides

Reduction of S O and SO2 to S, S–X to S–H, and P O to P

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B₂cat₂‐Mediated Reduction of Sulfoxides to Sulfides