Search

The intermediate oxidation state of sulfoxides is central to the plethora of their applications in chemistry and medicine, yet it presents challenges for an efficient synthetic access, limiting the structural diversity of currently available sulfoxides. Here, we report a data-guided development of direct decarboxylative sulfinylation that enables the previously inaccessible functional group interconversion of carboxylic acids to sulfoxides in a reaction with sulfinates. Given the broad availability of carboxylic acids and the growing synthetic potential of sulfinates, the direct decarboxylative sulfinylation is poised to improve the structural diversity of synthetically accessible sulfoxides. The reaction is facilitated by a kinetically favored sulfoxide formation from the intermediate sulfinyl sulfones, despite the strong thermodynamic preference for the sulfone formation, unveiling the previously unknown and chemoselective radicalophilic sulfinyl sulfone reactivity., (© 2022 Wiley-VCH GmbH.)

We present a convenient and efficient deoxygenation method for synthesizing disulfides and thioethers. The reaction involves an iodide-catalyzed reduction of methyl sulfinates or sulfoxides, respectively, employing formic acid as a stoichiometric reductant. The methodology demonstrates excellent yields and remarkable orthogonality towards other reducible functional groups. In silico explorations revealed the synergistic action of formic acid and in situ generated hydroiodic acid as Brønsted donors within a formic acid framework. This molecular arrangement activates the sulfinyl group and promotes subsequent deoxygenation. Notably, this approach enables the deoxygenation of sulfur-based functional groups using formic acid as the stoichiometric reductant without needing transition metals or strong acidic media such as hydroiodic acid. Overall, this methodology contributes to the advancement of the reduction of diverse oxygenated sulfur-containing compounds in a sustainable approach. [ABSTRACT FROM AUTHOR]

These results demonstrated that the direct reduction of sulfinyl sulfone by Hantzsch ester was not likely to happen and the necessity of both acetyl chloride and Hantzsch ester for the reuse of sulfonyl radicals. SP 1 sp H NMR (400 MHz, CDCl SB 3 sb ): = 7.67 (dd, I J i = 5.0, 1.4 Hz, 1 H), 7.64 (dd, I J i = 5.3, 1.3 Hz, 1 H), 7.39 (dd, I J i = 3.9, 1.4 Hz, 1 H), 7.23 (dd, I J i = 3.7, 1.3 Hz, 1 H), 7.10 (dd, I J i = 5.4, 3.7 Hz, 1 H), 7.04 (dd, I J i = 5.0, 3.8 Hz, 1 H). SP 1 sp H NMR (400 MHz, CDCl SB 3 sb ): = 7.61 (d, I J i = 8.4 Hz, 1 H), 7.58 (d, I J i = 2.1 Hz, 1 H), 7.51 (d, I J i = 8.5 Hz, 1 H), 7.39 (d, I J i = 2.2 Hz, 1 H), 7.30 (dd, I J i = 8.4, 2.2 Hz, 1 H), 7.25 (dd, I J i = 8.5, 2.1 Hz, 1 H). Keywords: sulfoxides; sulfinyl radicals; thiosulfonates; radical reaction; reductive coupling EN sulfoxides sulfinyl radicals thiosulfonates radical reaction reductive coupling 2487 2494 8 07/31/23 20230817 NES 230817 Graph Organosulfur compounds exist widely in natural products, agrochemicals, and pharmaceuticals, with sulfur being the fifth most used element in approved drugs followed by carbon, hydrogen, oxygen, and nitrogen. [Extracted from the article]

The intermediate oxidation state of sulfoxides is central to the plethora of their applications in chemistry and medicine, yet it presents challenges for an efficient synthetic access, limiting the structural diversity of currently available sulfoxides. Here, we report a data‐guided development of direct decarboxylative sulfinylation that enables the previously inaccessible functional group interconversion of carboxylic acids to sulfoxides in a reaction with sulfinates. Given the broad availability of carboxylic acids and the growing synthetic potential of sulfinates, the direct decarboxylative sulfinylation is poised to improve the structural diversity of synthetically accessible sulfoxides. The reaction is facilitated by a kinetically favored sulfoxide formation from the intermediate sulfinyl sulfones, despite the strong thermodynamic preference for the sulfone formation, unveiling the previously unknown and chemoselective radicalophilic sulfinyl sulfone reactivity. [ABSTRACT FROM AUTHOR]

Angesichts der Bedeutung von Carbonsäuren und Sulfoxiden für die medizinische Chemie, die Agrarwissenschaften und die organische Synthese wird die decarbonylierende Sulfinierung dem ungedeckten Bedarf an einer direkten Umwandlung zwischen den beiden funktionellen Gruppen gerecht und bietet Zugang zu einem neuen chemischen Raum an Sulfoxiden. Keywords: Carboxylic Acids; Radical Reactions; Sulfinates; Sulfoxides; Visible Light EN Carboxylic Acids Radical Reactions Sulfinates Sulfoxides Visible Light 1 1 1 10/21/22 20221024 NES 221024 B Eine decarbonylierende Sulfinylierung b wird von Oleg V. Larionov und Mitarbeitern in ihrem Forschungsartikel (e202210525) präsentiert, wie im Titelbild dargestellt. Angesichts der Bedeutung von Carbonsäuren und Sulfoxiden für die medizinische Chemie, die Agrarwissenschaften und die organische Synthese wird die decarbonylierende Sulfinierung dem ungedeckten Bedarf an einer direkten Umwandlung zwischen den beiden funktionellen Gruppen gerecht und bietet Zugang zu einem neuen chemischen Raum an Sulfoxiden. [Extracted from the article]

Allylsilanes underwent sila- ene reaction with sulfur dioxide in the presence of Lewis acid catalysts. The obtained Vogel’s silyl sulfinates were found to act as sulfinyl transfer agents in reactions with aryl, heteroaryl, alkyl, and allyl Grignard reagents proceeding with the expulsion of the trialkylsilyloxy group to give allyl sulfoxides in up to 83% yield. The nucleophilic attack of Grignard reagents was accelerated in toluene and in the presence of LiCl or ZnCl 2 as Lewis acidic additives. The developed method allows the transformation of allylsilanes into allyl sulfoxides. [ABSTRACT FROM AUTHOR]

A series of six-membered rings bearing cis oriented vicinal carboxylate and sulfinate esters were treated with Grignard reagents with the intention of transforming them to β-carboalkoxy substituted sulfoxides. The expected outcome did not transpire and instead the substrates demonstrated the capacity to accept 3 equiv. of organometallic agent in an uncontrollable manner. As such, the substrates possessing eclipsing carboxylate and sulfinate esters accepted two organic ligands at the carboxylate functionality and one at the sulfinyl group. When isomer mixtures of sterically encumbered sulfinate esters were reacted, a single sulfoxide stereochemistry resulted. A mechanism involving the intermediacy of a sulfurane is proposed to account for the experimental observations. [ABSTRACT FROM AUTHOR]

The Friedel-Crafts reaction of methyl alkyl- and arylsulfinates with aromatic systems, activated by one or more electron-donating substituents (OH, OMe, NHR, NR2), provides alkyl aryl and diaryl sulfoxides under mild conditions and in moderate to good yields. The very high regioselectivity usually observed in these sulfinylation reactions is rationalized on the basis of a Wheland intermediate having a trigonal bypyramidal structure in which steric and electronic interactions are significant factors strongly destabilizing the attack to the ortho positions. [ABSTRACT FROM AUTHOR]

A ligand with double sulfinyl groups, naphthyl-naphthalinesulphonylpropyl sulfoxide(dinaphthyl disulfoxide, L), was synthesized by a new method and its several lanthanide (III) complexes were synthesized and characterized by element analysis,molar conductivity, coordination titration analysis, IR, TG-DTA, 1HNMR and UV spectra. The composition of these complexes, were RE2(ClO4)6⋅(L)5⋅nH2O (RE=La, Nd, Eu, Tb, Yb, n=2~6, L=C10H7SOC3H6SOC10H7). The fluorescent spectra illustrated that the Eu (III) complex had an excellent luminescence. It was supposed that the ligand was benefited for transferring the energy from ligand to the excitation state energy level (5D0) of Eu (III). The Tb (III) complex displayed weak luminescence, which attributed to low energy transferring efficiency between the average triplet state energy level of ligand and the excited state (5D4) of Tb (III). So the Eu (III) complex displayed a good antenna effect for luminescence. The phosphorescence spectra and the relationship between fluorescence lifetime and fluorescence intensity were also discussed. [ABSTRACT FROM AUTHOR]

An abstract of the article "Mn(III)-Mediated Regioselective Synthesis of (E)-Vinyl Sulfones from Sodium Sulfinates and Nitro-Olefins" by B. Mosebach is presented.

The article discusses the development of the C2-symmetric chiral ligands, which play an important purpose in catalytic asymmetric reactions. It states that the C2-symmetric chiral ligands was made by using tert-butylsulfoxide which involves deprotonation, thiosulfinate, and flash chromatography purification. It adds that the development of C2-symmetric chiral ligands has resulted the matching adducts in good yields and excellent enantioselectivities.

Functionalized target compounds, required as synthons of natural products, pharmaceutical agents or in material science, are available in moderate to good yields in the presence of CuBr. [ABSTRACT FROM AUTHOR]

A graphical abstract of the article "Electrosynthesis of (E)-Vinyl Sulfones Directly from Cinnamic Acids and Sodium Sulfinates via Decarboxylative Sulfono Functionalization" by J. Su et al. is presented.

The efficient sulfonylation of N-(quinolin-8-yl)benzamide derivatives occurs at the C5 position generating environmentally benign byproducts by utilizing stable and safe sodium sulfinates as sulfide sources. [ABSTRACT FROM AUTHOR]

The abstract of the study "Iodine-Catalyzed Sulfonylation of Arylacetylenic Acids and Arylacetylenes with Sodium Sulfinates: Synthesis of Arylacetylenic Sulfones," by J. Meesin et al, is presented.

The article presents chemical equations for the article "A Radical Coupling Reaction of DMSO with Sodium Arylsulfinates in Air : Mild Utilization of DMSO as C1 Resource for the Synthesis of Arylsulfonyl Dibromomethane" by J. Shi and others, published in the journal "RSC Advances" in 2016.

The article discusses access to Sulfinates through Copper-Catalyzed Aerobic Oxidative Reaction of Alcohols with Sulfonyl Hydrazides.

A novel strategy to insert sulfonyl fragment into arenes is accomplished via an iron-catalyzed radical coupling reaction. [ABSTRACT FROM AUTHOR]

The unprecedented regioselective reaction of indoles with sodium sulfinates in the presence of iodide or copper catalysts affords C3- or C2-sulfonylindoles, respectively. [ABSTRACT FROM AUTHOR]

An abstract of the article "Copper-Mediated Sulfonylation of Aryl C(sp2)-H Bonds with Sodium and Lithium Sulfinates" by Shuai Liang and colleagues is presented.

A direct or two-step one-pot process for the coupling of boronic acids or aromatic BF3K salts with DABSO as SO2 source is developed to give sulfinic acid intermediates which react with alkyl bromides or a variety of carbon and nitrogen electrophiles to give unsymmetrical sulfones and sulfonamides. [ABSTRACT FROM AUTHOR]

Reaction of β-hydroxy gem-dibromides with aromatic sulfinates leads to α-bromosulfones in a diastereoselective manner. [ABSTRACT FROM AUTHOR]

The aerobic reaction of alkenes with sodium sulfinates (II) leads to hydroxysulfones. [ABSTRACT FROM AUTHOR]

An abstract of the article "Iodine-Mediated Synthesis of (E)-Vinyl Sulfones from Sodium Sulfinates and Cinnamic Acids in Aqueous Medium" by J. Gao and colleagues is presented.

β-Keto sulfones are synthesized through an electrochemical route by using ammonium iodide as the supporting electrolyte. The synthesis is promoted by the in situ electrogenerated iodine and affords the products in high to excellent yields under mild conditions. [ABSTRACT FROM AUTHOR]

An abstract of the article "Synthesis of Allyl Sulfoxides from Allylsilanes via Silyl Sulfinates" by A. Stikute and colleagues is presented.

A Pd(II)-catalyzed sulfonylation of both unactivated β-C(sp3)-H and γ-C(sp2)-H bonds with sodium arylsulfinates using an 8-aminoquinoline auxiliary is described. [ABSTRACT FROM AUTHOR]

affording vinyl sulfones under metal-free reaction conditions [ABSTRACT FROM AUTHOR]

An abstract of the article "Visible Light-Mediated Metal-Free Synthesis of Vinyl Sulfones from Aryl Sulfinates" by A. U. Meyer and colleagues is presented.

Copper ions are found to catalyze the [2,3]-sigmatropic rearrangement of propargylic sulfinates (I), (III), and (V) to allenic sulfones (II), (IV), and (VI), respectively. [ABSTRACT FROM AUTHOR]

A novel copper-mediated auxiliary-assisted ortho C-H bond sulfonylation of the benzoic acid derivative with a variety of sodium sulfinates is reported. [ABSTRACT FROM AUTHOR]

The in situ electrogenerated I2 effectively promotes this conversion to afford the target products in good yields. [ABSTRACT FROM AUTHOR]

An abstract of the article "Alkyl Sulfinates: Formal Nucleophiles for Synthesizing TosMIC Analogues" by J. A. Lujan-Montelongo et al. is presented.

The article presents chemical equations related to the article "Iodine-Catalyzed sp³ C—H Sulfonylation to Form β-Dicarbonyl Sulfones with Sodium Sulfinates" by W. C. Gao and colleagues, published in the ChemInform journal in the 2014 issue.

The article presents the chemical reaction of enantioenriched allylic alcohols by using sodium sulfinates.

The reaction of various (E)-configurated acid substrates with sulfinates (II) under conditions A) affords the pharmaceutically important vinyl sulfones as exclusive (E)- isomers. [ABSTRACT FROM AUTHOR]

Optimal conditions are elaborated for the preparation of a broad spectrum of intermediate ammonium sulfinates [cf. [ABSTRACT FROM AUTHOR]

An abstract of the article "Copper-Catalyzed Aerobic Decarboxylative Sulfonylation of Cinnamic Acids with Sodium Sulfinates: Stereospecific Synthesis of (E)-Alkenyl Sulfones" by Q. Jiang and colleagues is presented.

The reaction can be scaled up. [ABSTRACT FROM AUTHOR]

The article presents a chemical equation for the article "Application of Fundamental Organometallic Chemistry to the Development of a Gold-Catalyzed Synthesis of Sulfinate Derivatives" by M. W. Jonson and colleagues published in "Angewandte Chemie International Edition" in 2014.

The reaction of propargylic bromides with sodium arylsulfinates in the presence of Pd-C and Bu4NF is described to give 2,3-bissulfonylpropenes (III) or (V) in good yields. [ABSTRACT FROM AUTHOR]

Oxygen or DMSO act as oxidants in this copper-catalyzed reaction. [ABSTRACT FROM AUTHOR]

The presented reaction is compatible with a wide range of functional groups in arylsulfinates (I) expanding the scope of Cu-catalyzed electrophilic triflouromethylation reactions. [ABSTRACT FROM AUTHOR]