Sodium Phenylsulfinate Research Articles

Copper-Catalyzed Vicinal Thiocyanosulfonylation of Alkenes and Alkynes.

Efficient copper-catalyzed radical thiocyanosulfonylation of alkenes and alkynes with potassium thiocyanate and sodium phenylsulfinate is described. The reactions provide general and convenient methods toward the synthesis of β-thiocyanoalkyl sulfones and β-thiocyanoalkenyl sulfones, respectively, in satisfactory yields. Based on conducted mechanistic experiments, a mechanism involving oxidative generation of sulfonyl radicals and subsequent addition to alkenes followed by Cu-assisted thiocyanation is proposed. Moreover, the practicability of the reaction is successfully demonstrated by its successful application on a gram scale.

Facile, mild and efficient synthesis of azines using phosphonic dihydrazide

Several bis(N'-arylpropanehydrazonoyl chlorides) were synthesized in good yields from condensation reactions of hydrazonoyl chlorides and phosphonic dihydrazide. Under the conditions employed, none of the expected phosphorylhydrazines were isolated. Nucleophilic substitution of bis(N'-arylpropanehydrazonoyl chlorides) with thiophenol, sodium phenylsulfinate, hydroxyl amine, and piperidine afforded the corresponding azines. Similarly, 1,2-bis(heteroaryl)ethylidene)hydrazines were produced from reaction of phosphonic dihydrazide and heteroaryl methyl ketones. The structures of the products were confirmed by NMR and IR spectral data along with X-ray crystal structure determination and their purities were confirmed by the elemental analyses.

Metal‐Free Iodosulfonylation of Internal Alkynes: Stereodefined Access to Tetrasubstituted Olefins

AbstractThe stereoselective E‐iodosulfonylation of internal alkynes for synthesizing highly defined tetrasubstituted olefins using sodium phenyl sulfinate and iodine has been achieved. Most of the alkynes explored are non‐symmetrical and the regioselection is under full control. Arylalkynes with various electron‐withdrawing groups like keto, aldehyde, ester, amide, cyano, sulfone, bromo, chloro and iodo on the other end are identified as successful precursors to yield the highly functionalized olefins. Alkynes directly tethered with heteroatoms are also found to be suitable substrates.magnified image

4-Phenylsulfonyl-2,3,5,6-tetrachloropyridine: synthesis and synthetic utility

4-Phenylsulfonyl-2,3,5,6-tetrachloropyridine was synthesized from the reaction of sodium phenylsulfinate with pentachloropyridine in optimized reaction condition. The reaction of some mono- and bidentate N and O nucleophiles with 4-phenylsulfonyl-2,3,5,6-tetrachloropyridine was studied in order to assess the impact of electron-withdrawing functional group (PhSO2−) upon regiochemistry of aromatic nucleophilic substitution. Substitution generally occurs at 4-position of pyridine ring, by less steric hindrance nucleophiles although mixtures of products (ortho- and para-substituted) are obtained with more steric hindrance cases. The structures of all the compounds were confirmed by IR, 1H NMR and 13C NMR spectroscopy as well as elemental analysis and X-ray crystallography.

Aerobic Palladium-Catalyzed Arylation of Alkenes Using Sodium Sulfinates

Palladium-catalyzed oxidative arylations of terminal alkenes could be performed using sodium sulfinates at 60 °C in air. The procedure gave various aryl alkenes after the desulfonylation of sodium arylsulfinates in the presence of a palladium catalyst. For instance, the reaction of styrene with sodium phenylsulfinate afforded <i>trans</i>-1,2-diphenylethylene in 80% yield without the formation of other stereoisomers.

Polyfunctional Tetrahydropyrido[2,3‐b]pyrazine Scaffolds from 4‐Phenylsulfonyl Tetrafluoropyridine.

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Polyfunctional Tetrahydropyrido[2,3-b]pyrazine Scaffolds from 4-Phenylsulfonyl Tetrafluoropyridine

[Reaction: see text]. Polyfunctional tetrahydropyrido[2,3-b]pyrazine scaffolds can be synthesized by sequential reaction of pentafluoropyridine with sodium phenylsulfinate and an appropriate diamine. The polyfunctionality possessed by the difluorinated tetrahydropyrido[2,3-b]pyrazine scaffolds was demonstrated in selected model reactions with nucleophiles to give access to various polysubstituted [6,6]-ring fused systems.

A New Synthesis of β‐Amino Acids by Use of Ketene Diethyl Acetal as Enolate Equivalent.

AbstractFor Abstract see ChemInform Abstract in Full Text.

A new synthesis of β-amino acids by use of ketene diethyl acetal as enolate equivalent

Reaction of phenylsulfonyl formamides, readily available in a single step from an aromatic aldehyde and sodium phenylsulfinate, with ketene diethyl acetal under basic conditions gives N-formyl β-amino acid esters in good yield, which can be kinetically resolved with a lipase.

Towards Asymmetric Catalysis in the Major Groove of 1,1′-Binaphthalenes

Four new diphosphane ligands, (R)-4, (R)-5, (S)-6, and (R)-7 (Schemes 3, 4, 6, and 7), featuring metalcoordination sites located in the major groove of chiral 1,1′-binaphthalene clefts, were prepared in enantiomerically pure form. The performance of this new class of ligands was tested in enantioselective, Pd-catalyzed allylic alkylation reactions with acyclic and cyclic methyl carbonates 28 – 30 as substrates under various reaction conditions (Schemes 8 and 9). Using sodium phenyl sulfinate as a nucleophile, the reactivity of the catalysts formed with the new ligands and suitable palladium precursors was found satisfactory (>90%); however, the ee values were in all cases poor (<4%). Slightly better results were obtained using anions of dimethyl malonate as nucleophiles, but, also in these cases, the ee values never exceeded 17% (Table). 31P-NMR-Spectroscopic investigations revealed the formation of multiple-catalyst species in solution (Fig. 2), and molecular modeling suggested a lack of embedding of the coordinated substrate in a `chiral pocket' (Fig. 3), which probably accounts for the observed low level of enantioselectvity.

KINETICS OF THE INTERACTION BETWEEN 2-NITROETHENYLBENZENE AND SOME S-CONTAINING NUCLEOPHILES

Abstract The kinetics of the reaction of 2-nitroethenylbenzene with sulfur-containing nucleophilic reagents such as sodium phenylsulfinate, sodium thiosulfate, sodium bisulfite, sodium sulfide, sodium thiophenolate, and sodium thioglycolate was studied by means of UV spectroscopy. The change in the nucleophilic reactivity of these nucleophiles depending on their basicity was studied. The reactions can be expressed by a second-order kinetic equation. Rate constants, activating energy and enthalpy of activation were calculated at 288–308 K.

ChemInform Abstract: Alkylation of Sodium Phenylsulfinate on Alumina. Activation by Microwaves or Ultrasounds.

AbstractThe halides (I) are coupled with the sodium sulfinate (II) supported on neutral alumina to produce the sulfones (III).

Alkylation of Sodium Phenylsulfinate on Alumina. Activation by Microwaves or Ultrasounds

Abstract Organic halides absorbed without solvent onto sodium phenylsulfinate on alumina (1) gave phenylsulfones (2) under microwave or ultrasound activation.

ChemInform Abstract: Generation and Cycloaddition Reactions of Phenylsulfonyl‐Substituted 1,3‐Butadienes.

AbstractThe alkynyl phenyl sulfone (I) is consecutively treated with LDA and methyl iodide (II) to form the allene (III) which reacts with sodium phenylsulfinate (IV) to produce the 1,2‐disulfonyl‐2‐butene (V).

Preparation and alkylation reactions of 4-nitrobenzyl and 5-nitrofurfuryl sulfones

Substitution reaction of 5-nitrofurfuryl bromide (I) with sodium thiophenoxide and 4-chlorothiophenoxide in dimethyl sulfoxide at 20 °C and oxidation with dimethyl sulfoxide in the reaction medium afforded 5-nitrofurfuryl phenyl sulfone (IVa) and 5-nitrofurfuryl 4-chlorophenyl sulfone (IVb), respectively. Similarly, 4-nitrobenzyl bromide reacted with sodium 4-chlorothiophenoxide to give 4-nitrobenzyl 4-chlorophenyl sulfone (VII) and with sodium phenylsulfinate to afford 4-nitrobenzyl phenyl sulfone (IX). The sulfide intermediates were not isolated. The sulfone IX was used as substrate in alkylation reactions, catalysed by polyethylene glycols. Derivatives IVb and VII were identified by IR and mass spectroscopy, alkylation products by 1H NMR spectroscopy.

The michael induced ramberg-bäcklund homologation to conjugated isoprenoids

Treatment of the sulfones 1 or 2 with sodium phenylsulfinate in DMSO affords the head-to-tail coupled conjugated monoterpenoids 5–8 in comparable amounts. The corresponding reaction of 3 gives the isomers 16 and 17. The tail-to-tail homologation of 4 furnishes chiefly a 2 E,4 E/Z-mixture of the conjugated isoprenoids 18 and 19. The various isoprenoid mixtures are separated into their components and the configuration of the isomers is established by 1H NMR double resonance and the NMR/NOE technique. The head-to-tail and tail-to-tail coupled isoprenoid mixtures 5–8 and 18–21, respectively, are isomerized to 2 E/Z, 4 E-mixtures in a 2:1 ratio. The C 15-sulfones 11 and 13 are obtained by treatment of 1 with the head-functionalized isoprene synthon 10. Some speculations on the stereochemical course of the MIRB-homologation are presented.

Sulfur Dioxide Insertion Reactions of some Compounds containing Sn—C and Fe—Sn—C Bonds

The preparations of [CpFe(CO)2]2Sn[OS(O)Ph]2, CpFe(CO)2SnPh[OS(O)Ph]2, CpFe(CO)2SnPh[OS(O)Ph]OH, and Ph2Sn[OS(O)Ph]2 by sulfur dioxide insertion into the C—Sn bond and also by reaction of the sodium phenyl sulfinate with the corresponding chloro-compounds are reported. The infrared (i.r.) spectra and some reactions of these compounds are also discussed.