Methyl sulfoxide sulfonic esters

Pedersen and coworkers investigated the El mass spectra of several 2-hydroxyphenyl alkyl sulfones (39) and sulfoxides (Section II.B). The methyl derivative seemed to fragment only via sulfinate ester formation giving the primary product ions m/z 157 and 109 (equation 14). Obviously hydrogen bonding between the ortho hydroxyl and the sulfone sulfur makes the loss of CH3SO2 difficult in contrast to the situation in methyl phenyl sulfone. The sulfinate ester rearrangement is not important when R>Et in 39. 

Purification of the crude mixture was performed by flash chromatography to afford pure 5-(l-hydroxyethyl)-2-methyl-3-furoic acid 5a-cholestan-3(3-yl ester (86% yield), 4-bromophenyl methyl sulfone (59% yield) and (R)-4-bromophenyl methyl sulfoxide (34 % yield). 

At an early date it was already recognized that the ketone (IX) derived from an oxidation of the C-18 carbinol function of methyl reserpate could be of considerable utility for further transformation of the reserpine pentacyclic ring system, but early attempts at the preparation of the desired compound by conventional oxidation, e.g., by Oppenauer s method, AAchlorosuceinimide, sodium dichromate, or chromic oxide in pyridine, were unsuccessful with both methyl reserpate and methyl 18-epireserpate. The ketone was finally obtained by heating methyl reserpate p-bromobenzene sulfonate with dimethyl sulfoxide in the presence of triethylamine (162), a method successfully used for simpler compounds (163). Subsequently, it was found that this oxidation could also be realized with other benzene sulfonate esters of methyl reserpate and 18-epireserpate. That the stereochemistry of the molecule was unaffected was proved by sodium borohydride reduction of the ketone, which gave equal amounts of methyl reserpate and its 18-epimer. This and other simple reactions of the ketone are sketched in Chart III, and additional observations will be given. 

Methyl Methylthiomethyl Sulfone. Methyl methyl-thiomethyl sulfone is the 5-methyl analog of MT-sulfone and it is conveniently synthesized by oxidation of methyl methylthiomethyl sulfoxide (FAMSO) with potassium permanganate or H202-Na0H. It is useful for synthetic methods similar to those using MT-sulfone synthesis of carboxylic esters, ketones, and a-aLkoxy- -arylacetates. In the reaction of this reagent with allylic bromides, a-methylthio- /,5-unsaturated sulfones are obtained by stirring the bromide with potassium carbonate and potassium iodide in hexamethylphosphoric triamide (eq 14), which does not occur with MT-sulfone. 

Other carbanionic groups, such as acetylide ions, and ions derived from a-methylpyridines have also been used as nucleophiles. A particularly useful nucleophile is the methylsulfinyl carbanion (CH3SOCHJ), the conjugate base of DMSO, since the P-keto sulfoxide produced can easily be reduced to a methyl ketone (p. 549). The methylsulfonyl carbanion (CH3SO2CH2 ), the conjugate base of dimethyl sulfone, behaves similarly, and the product can be similarly reduced. Certain carboxylic esters, acyl halides, and DMF acylate 1,3-dithianes (see 10-10. )2008 Qxj(jatjye hydrolysis with NBS or NCS, a-keto aldehydes or a-... 

The reaction of alcohols with CO was catalyzed by Pd compounds, iodides and/or bromides, and amides (or thioamides). Thus, MeOH was carbonylated in the presence of Pd acetate, NiCl2, tV-methylpyrrolidone, Mel, and Lil to give HOAc. AcOH is prepared by the reaction of MeOH with CO in the presence of a catalyst system comprising a Pd compound, an ionic Br or I compound other than HBr or HI, a sulfone or sulfoxide, and, in some cases, a Ni compound and a phosphine oxide or a phosphinic acid.60 Palladium(II) salts catalyze the carbonylation of methyl iodide in methanol to methyl acetate in the presence of an excess of iodide, even without amine or phosphine co-ligands platinum(II) salts are less effective.61 A novel Pd11 complex (13) is a highly efficient catalyst for the carbonylation of organic alcohols and alkenes to carboxylic acids/esters.62... 

Although methyl 4-oxotetrahydrothiopyran-3-carboxylate and the corresponding 2,3-dihydro-4//-thiopyran-4-one exist as a mixture of keto and enol forms in solution, the 2,3-dihydro sulfoxide is present only as the ketone. However, the sulfone and the tetrahydro sulfoxide and sulfone are present exclusively in the enolic form. The picture is further complicated in the solid state, where the dihydro compound and its sulfoxide exist exclusively as the keto structure but the sulfone is found as the enol (Table 27) <1986J(P2)1887>. The related 2-esters of tetrahydrothiopyran-3-one 268 exist as a ca. 1 2 mixture of keto and enol <1981T2633>. 

Under the same basic conditions /ra . -l-acetoxymethyl-1-methyl-2-tosylcyclopropane generated an a-sulfonyl anion, which attacked the ester group intramolecularly and afforded 2,5-dimethyl-l-tosyl-3-oxabicyclo[3.1.0]hexan-2-ol (22) in 50% yield.Stereoselective synthesis with a chiral cyclopropyl sulfoxide was experienced when ( )-4-tolylsulfinylcyclopropane was reacted first with butyllithium and then with methyl benzoate and gave 1-benzoyl-1-[(5)-4-tolylsulfinyl]cyclopropane (23a) in 62% yield. A useful reaction took place when 2-(hy-droxymethyl)cyclopropyl phenyl sulfide was treated first with an excess of butyllithium and then with dimethylformamide and gave 2-hydroxy-l-phenylsulfanyl-3-oxabicyclo[3.1.0]hexane (24), a lactol which has been used to carry out various useful synthetic transformations. Another useful reaction occurred when cyclopropyl phenyl sulfones were treated with butyllithium followed by an acyl imidazole to give acyl cyclopropanes in decent yield. 

An interesting observation can be made by comparing some of our results with the previous study carried out by Noyori. Removal of one oxygen in the EWG on the dienophile results in a dramatic increase in the exo/endo selectivity [Table 3(b)]. Thus, changing the EWG on the dienophile from a methyl ester (COOMe) to a methyl ketone (COMe) or replacing a sulfone (SOjPh) with a sulfoxide (SOPh) results in a 10 to 20-fold improvement in the exo/endo selectivity. 

Papain catalyzed the polymerization of L-methionine methyl ester hydrochloride to give water-insoluble oligomer with DP = 8-10 (59-61). The resulting water-insoluble oligomer was converted to water-soluble sulfoxide and sulfone derivatives by treatment of DMSO or hydrogen peroxide. Esters of phenylalanine. 

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