Oxidative cleavage sulfonation

Oxidative cleavage of oxosulfonium ylides490 as well as of sulfoximines491 leads to sulfone formation. In the course of oxidations of dialkoxy sulfuranes(IV) by hydrogen peroxide492 or f-butyl hydroperoxide493, sulfone formation takes place (equation 99). 

According to Marshall [23] and Beech [26], the oxidation of the thiophenol linker would increase the reaction rate. To study this effect, the linker in resin (35) was oxidized to sulfone/sulfoxide using mCPBA. Cleavage reaction of resin (35) -OX with n-butylamine went to completion in less than 4 min (Fig. 12.20), compared with 24 h needed for this resin under the same conditions without oxidation. The rate constant was determined to be 0.0179, which was a 580-fold increase compared with the unoxidized form. This result indicated that a linker oxidation was preferred for high yield when the products will not be affected by oxidation conditions. 

Potassium nitrosodisulfonate, 258 Trimethylsilyl chlorochromate, 327 By hydrolysis of acetals or thioacetals Amberlyst ion-exchange resin, 152 Methylthiomethyl p-tolyl sulfone, 192 By isomerization of allylic alcohols N-Lithioethylenediamine, 157 By oxidation of aromatic side chains Trimethylsilyl chlorochromate, 327 From oxidative cleavage of alkenes [Bis(salicylidene-7-iminopropyl)-methylamine]cobalt(II)... 

From oxidative cleavage of 1,2-diols and 1,2-amino alcohols Dibutyltin oxide, 95 By reaction of alkyl halides with sulfur-stabilized carbanions Methylthiomethyl p-tolyl sulfone, 192 From reduction of carboxylic acids Vilsmeier reagent, 341 From terminal alkenes by addition reactions... 

The alkylation products are synthetically useful because simple subsequent transformations furnishes precursors of important natural products as illustrated in Scheme 8E.23. Simple oxidative cleavage of allylic phthalimide 45 generates protected (5)-2-aminopimelic acid, whose dipeptide derivatives have shown antibiotic activity. The esterification via deracemization protocol is not limited to the use of bulky pivalic acid. The alkylation with sterically less hindered propionic acid also occurs with high enantioselectivity to give allylic ester 116, which has been utilized as an intermediate towards the antitumor agent phyllanthocin and the insect sex excitant periplanone. Dihydroxylation of the enantiopure allylic sulfone gives diol 117 with complete diastereoselectivity. Upon further transformation, the structurally versatile y-hydroxy-a,(f-un-saturated sulfone 118 is readily obtained enantiomerically pure. 

Oxidation. The range of oxidation potential of HOF-MeCN has been extended to the direct preparation of epoxy carboxylic acids from alkenoic acids, oxidative cleavage of methyl ethers to ketones, and conversion of aryl perfluoroalkyl sulfides to the sulfones. ... 

To summarize, sulfonic acid is the principal established end product of the oxidative cleavage of the disulhde bond from the chemical bleaching of human hair with current hair bleach products [3,9]. The mercaptan content of bleached hair is lower than that of unbleached hair [4], The intermediate oxidation products of cystine (i.e., the disulhde monoxide, dioxide, trioxide, and tetroxide) do not exist as signihcant end products of hair bleaching using today s commercial bleach products [3,6,9]. Nevertheless, evidence has been presented demonstrating low levels of cystine oxides in bleached hair [2],... 

Oxidative Cleavage of Polymer-bound Sulfoximines. Oxidative cleavage of a Merrifield resin-bound sulfoximine afforded the corresponding sulfone in high yield (eq 27). The reaction proceeds by the formation of the V-oxide that reacts with a second equivalent of the peracid to lead to the sulfone and the polymer-bound nitroso derivative. 

Two routes have gained industrial prominence to produce 2-naphthol, namely alkali fusion of sodium naphthalene-2-sulfonate and the oxidative cleavage of 2-isopropylnaphthalene. 

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