Sulfone, benzyl phenyl

Dimetal derivatives 283 of alkyl and benzyl phenyl sulfones were found to react with aldehydes or ketones to give a, /J-unsaturated phenyl sulfones 284 in good yields366. 

We suggest that the structure of lithiated 48, as shown by structure 48a (only the monomeric species is considered) in Scheme 2, may be similar to that of lithiated benzyl phenyl sulfone.53 One would expect the benzylic carbon of 48a to be close to planar and the phenyl substituent to be anti to the bulky Wfert-butyldiphenylsilyl moiety. The nonbonding orbital at the benzylic carbon would be approximately coplanar with the S-CH3 a bond as a result of a stabilizing nc-a s-c interaction. Electrophilic attack on 48a should occur from the less hindered diastereoface, i.e., anti to the S-CH3. An open transition state 53 in which R of the aldehyde and the phenyl substituent of 48a are anti is consistent with the stereochemical outcome. 

Steroidal sulfides are converted into optically active sulfoxides by Ca-lonectria decora [1052] and by Rhizopus stolonifer [1048]. Aspergillus niger transforms benzyl phenyl sulfide into optically active benzyl phenyl sulfoxide in 23% yield and into benzyl phenyl sulfone in 9% yield [1048]. 

It should be noted that the crystal structure of the Li/TMEDA salt of benzyl phenyl sulfone reported by Boche is conceptually similar to the theoretical structure (122). X-Ray structure determination of a-(phenylsulfonyl)benzyllithium-TMEDA, a-(phenylsulfonyl)allyllithium and the potassium salt of bis(methylsulfonyl)-3-(2,6-dimethyoxypyridyl)sulfonylmeAane shows that the coordination about the anionic carbon atom is nearly planar, and that the p-orbital on the anionic carbon is approximately gauche to the two oxygen atoms on the sulfur. " The anionic caibon atom can be described as interacting with the sulfur atoms in an ylide-like manner with a hairier to rotation about the "C—SO2 bond. 

The few examples indicate that sulfone-stabilized carbanions should react normally with electrophilic animating reagents (Eqs. 145158 and 146465) with the caveat that free a-amino sulfones are unstable.158,465 The (3,y-unsaturated sulfone 74 is animated at the y-position (Eq. 147),250 presumably by an ene reaction. The preparation of a-tosyl azides from nitronates was shown above in Eq. 144. The scope of this reaction does not seem to have been determined. Reaction of the anions of nitrobenzyl aryl sulfones with l-oxa-2-azaspiro[2.5]octane (13a) gives nitrobenzaldehydes by cleavage of the initially formed amination products.466 Similarly, reaction of the lithium salt of benzyl phenyl sulfone with phenyl azide gives benzilydeneaniline and phenyl sulfinate.467 No reports on animations of sulfoxide-stabilized carbanions were found. 

Decyl-phenyl- und -(2,4,6-trimethyl-phenyl)-sulfon werden durch Lithium/Methyl-amin zu Decansulfinsaure (95 bzw. 80% d.Th.) und Benzol bzw. Mesitylen (55% d.Th.) reduziert1. Methyl-phenyl-sulfon und Benzyl-phenyl-sulfon ergeben mit Natriumamal-gam in siedendem Athanol Benzolsulfinsaure2. 

This reaction was initially reported by Eisleb in 1941. It is the alkylation of compounds of active hydrogen with alkyl halide via the treatment of sodium amide. The compounds with active hydrogens include deoxybenzoin, diphenylmethane, phenylacetonitrile, fluorene, " benzyl phenyl sulfone, and 2-pyridyl acetonitrile. This reaction normally gives a satisfactory yield of introducing A/, A/ -dialkylamino alkyl group to compounds with an active proton. ... 

The rearrangement of furfuryl benzenesulfinate (1) appears of special interest. In contrast with the corresponding benzyl ester, this sulfinate was found to undergo a facile rearrangement to sulfone. Furthermore, in nonhydroxylic solvents a mixture of furfuryl phenyl sulfone (2) and 2-methyl-3-furyl phenyl sulfone (3) is obtained (equation 6)40. 

Auch sterische Aspekte konnen eine Rolle spielen. So erhalt man z. B. in DMF/Tetra-butylammoniumperchlorat bzw. in Methanol/Tetramethylammoniumchlorid in geteilter Zelle an Quecksilber aus Methyl-(2-methyl-phenyl)-sulfon 2-Methyl-benzolsulfinsaure (bis 93% d. Th.) bzw. aus Methyl-(2-tert.-butyl-phenyl)-sulfon Methansulfinsaure (bis 91% d. Th.). (2-tert.-Butyl-phenyl)-benzyl-sulfon wiederum wird zur 2-tert.-Butyl-ben-zolsulfinsaure (86% d. Th.) gespalten5. 

Directed lithiation of aromatic compounds is a reaction of broad scope and considerable synthetic utility. The metalation of arenesulfonyl systems was first observed by Gilman and Webb and by Truce and Amos who reported that diphenyl sulfone is easily metalated at an orf/io-position by butyllithium. Subsequently, in 1958, Truce and coworkers discovered that metalation of mesityl phenyl sulfone (110) occurred entirely at an orf/io-methyl group and not at a ring carbon, as expected. Furthermore, refluxing an ether solution of the lithiated species resulted in a novel and unusual variation of the Smiles rearrangement and formation of 2-benzyl-4,6-dimethyl-benzenesulfinic acid (111) in almost quatitative yield (equation 78). Several other o-methyl diaryl sulfones have also been shown to rearrange to o-benzylbenzenesulfinic acids when heated in ether solution with... 

Initially, the allylation reaction was studied with the /V-benzyloxycarbonylamino sulfone derived from benzaldehyde and benzoyloxycarbonyl (Cbz) carbamate (Scheme 1, R1 = Ph, R = Bn). Various catalysts were screened for the allylation of benzyl phenyl(phenylsulfonyl)methylcarbamate la with allyltrimethylsilane in dichloromethane (Table 1). Among the various Bi catalysts tested, Bi(OTf)3 4H20 was shown to be the most efficient (Table 1, entry 5). BiCl3, BiBr3, Bi(OAc)3, or Bi(OCOCF3)3 did not allow the reaction to proceed and starting material was... 

Catalytic oxidations of sulfides were carried out in 1,2-dichloroethane with cumyl hydroperoxide by using 10 mol % of the catalyst. The best enantioselectivity was achieved with complex 6c. However, sulfone was always produced as byproduct of the reaction. Even with a limited amount of hydroperoxide, the sulfone formation could not be avoided. For example, the reaction of methyl p-tolyl sulfide using 0.5 mol equiv. of cumyl hydroperoxide with respect to sulfide gave a 62 38 mixture of the corresponding (.S j-sulfoxide and sulfone. The reaction of benzyl phenyl sulfide led to the formation of (5)-sulfoxide (84% ee) and sulfone ([sulfox-ide]/[sulfone] = 77 23). It was established that sulfone was produced from the early stages of the reaction. It was also demonstrated that some kinetic resolution of the sulfoxide cooperated with the enantioselective oxidation of the sulfide. A unique feature of this oxidation system, as compared to those using various Ti(IV)/(DET) complexes, is the insensitivity of the enantioselectivity (40-60% ee at 0°C) to the nature of the alkyl group of sulfides Ar-S-alkyl. 

Neutral alumina (1.5 g) was thoroughly mixed with iodobenzene diacetate (532 mg, 1.65 mmol) and benzyl phenyl sulfide Id (300 mg, 1.5 mmol) using a pestle and mortar. The adsorbed material was placed in an alumina bath inside the microwave oven and irradiated at 50% power for two successive intervals of 45 s each (with time interval of 3-4 min bath temperature rose to 80-85 °C). The progress of the reaction was monitored by TLC (hexane-ethyl acetate, 7 3, v/v). When the reaction was complete the whole material was directly charged onto a silica gel column which provided iodobenzene on elusion with hexane (100 mL). The fractions eluted by chloroform-hexane (1 1 v/v) provided sulfone (<7% by... 

Keywords benzyl phenyl sufone, / -cyclodextrin, photorearrangement, 2-methyl-phenyl phenyl sulfone... 

Cyclopropyl phenyl sulfones. 3-Bromo-l-(phenylsultonyl)-l-propene (1), prepared as shown, reacts with allyl, propargyl, aryl, and benzyl Grignard reagents to give (E)-2-substituted cyclopropyl phenyl sulfones (2) in moderate to good yield. This reaction is not observed with alkyl Grignard reagents. 

If the electron-withdrawing group is such that self-condensation does not occur then the anion can be generated in the normal manner. Thus, the anion 349 of cyclopropyl phenyl sulfone (348) can be readily prepared by treatment of the parent compound with n-butyllithium at 0°C in THF. The anion has been shown to condense in excellent yield with aldehydes, ketones, methyl iodide and allyl and benzyl bromides to yield 350. The... 

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