Sulfonyl chloride arylation

An aryl methane- or toluenesulfonate ester is stable to reduction with lithium aluminum hydride, to the acidic conditions used for nitration of an aromatic ring (HN03/H0Ac), and to the high temperatures (200-250°) of an Ullmann reaction. Aryl sulfonate esters, formed by reaction of a phenol with a sulfonyl chloride in pyridine or aqueous sodium hydroxide, are cleaved by warming in aqueous sodium hydroxide. ... 

Another point for structural diversification is the sulfonamide group. Imai had already shown that a wide variety of groups could be introduced at this position to optimize the reaction. Since a wide variety of sulfonyl chlorides are commercially available, a number of different types of groups could be examined (Scheme 3.34). Testing of a variety of aryl and alkyl groups on the 1,2-cyclohexanediamine backbone demonstrates that the simple methanesulfonamide 122 is clearly superior or equal to many other analogs in the cyclopropanation of cinnamyl alcohol (Table 3.11). Another concern which was directly addressed by this survey was the question of catalyst solubility. 

Whereas aryl Grignard compounds afford good yields of sulfones with sulfonyl fluorides298 299, phenyllithium is mainly chlorinated by a-toluene-sulfonyl chloride on the other hand, the corresponding fluoride yields only a trace of the expected mono-sulfonylation product, while the main product is 26 obtained by twofold sulfonylation300 (equation 61). 

The copper-catalyzed additions of sulfonyl chlorides to conjugated dienes and trienes73 as well as to aryl-substituted cyclic olefins74 and substituted styrenes have been described75 for example, arenesulfonyl chlorides add to vinylarenes providing good to excellent yields75 of /J-chlorosulfones ... 

Sulfonyl chlorides as well as esters and amides of sulfonic acids can be hydrolyzed to the corresponding acids. Sulfonyl chlorides can by hydrolyzed with water or with an alcohol in the absence of acid or base. Basic catalysis is also used, though of course the salt is the product obtained. Esters are readily hydrolyzed, many with water or dilute alkali. This is the same reaction as 10-4, and usually involves R —0 cleavage, except when R is aryl. However, in some cases retention of configuration... 

Diaryl sulfones can be formed by treatment of aromatic compounds with aryl sulfonyl chlorides and a Friedel-Crafts catalyst. This reaction is analogous to Friedel-Crafts acylation with carboxylic acid halides (11-14). In a better procedure, the aromatic compound is treated with an aryl sulfonic acid and P2O5 in polypho-sphoric acid. Still another method uses an arylsulfonic trifluoromethanesulfonic anhydride (ArS020S02CF3) (generated in situ from ArS02Br and CF3S03Ag) without a catalyst. ... 

Reaction of 3-phenyl-1,2,4-thiadiazole-5-thiol (10) (R = Ph) with formaldehyde and with aryl-sulfonyl chlorides leads to N-4 derivatives (26) and (27) (Scheme 8) <89MI 408-01 >. 

Recently, sulfinyl and sulfonyl peroxy radical intermediates 6a and 6b have been prepared by the reactions of aryl sulfinyl or sulfonyl chloride with superoxide anion radical, respectively. These peroxy intermediates show strong oxidizing abilities in various oxidations. This chapter will describe the properties and applications of a variety of sulfur and phosphorus peroxy compounds in oxidation reactions. For a more complete picture, readers should consult the original papers cited in the areas that most interest them. 

Mahyisulfonyl chloride CH3SO2CI and tosyl chloride give low to moderate yields of ROCSO2CH3 and RC=CS02-Aryl. Part of the sulfonyl chloride reacts with the lithium alkynylide to give a chloroalkyne. A more succesful method to prepare acetylenic sulfones involves Oxidation of acetylene sulfides with peiacids. 

Benzoxepins are frequently synthesized by cyclization of alkyl aryl or diaryl ether precursors. An intramolecular Wittig reaction (equation 48) is used to provide the ring closure step in the synthesis of 1-benzoxepin (28) (68JOC2591). An internuclear cyclization reaction of an aromatic sulfonyl chloride (equation 49) occurred upon heating (250 °C) in the presence of a copper chloride catalyst to yield tribenz[6,d,/]oxepin (175). The analogous thiepin (see equation 71) may also be synthesized by this route (65T1299). 

S-bonded alkyl and aryl sulfinato complexes can be prepared by the reaction of sulfonyl chlorides with Pt(C2H4)(PPh3)2,1633 the phase-catalyzed reaction of PtCl with NaS02R, 4 or the insertion of S02 into a platinum-alkyl bond1635 as shown in equations (481)-(483). When PtCl(S02R)L2 is treated with silver ion the 0,0 -bonded chelate complex (173) is formed (equation 484). 

A number of methods for the preparation of vinyl and allyl sulfones are available [1U9, 110], and the syntheses of vinyl sulfones from alkenes has been reviewed [116]. A simple one-step procedure of wide applicability makes use of a palladium-catalysed cross-coupling reaction between aryl and alkyl sulfonyl chlorides and substituted vinyl and allyl stannanes... 

Arylation with suffinate salts and sulfonyl chlorides 858... 

Mesylates are used for Ni-catalysed reactions. Arenediazodium salts 2 are very reactive pseudohalides undergoing facile oxidative addition to Pd(0). They are more easily available than aryl iodides or triflates. Also, acyl (aroyl) halides 4 and aroyl anhydrides 5 behave as pseudohalides after decarbonylation under certain conditions. Sulfonyl chlorides 6 react with evolution of SO2. Allylic halides are reactive, but their reactions via 7t-allyl complexes are treated in Chapter 4. Based on the reactions of those pseudohalides, several benzene derivatives such as aniline, phenol, benzoic acid and benzenesulfonic acid can be used for the reaction, in addition to phenyl halides. In Scheme 3.1, reactions of benzene as a parent ring compound are summarized. Needless to say, the reactions can be extended to various aromatic compounds including heteroaromatic compounds whenever their halides and pseudohalides are available. 

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