Oxime sulfonyl

This presumably forms oxime, 120, on reaction with hydroxylamine that intermediate is not isolated as it cyclizes spontaneously to the isoxazole, 121. Acylation of the isoxazole with the sulfonyl chloride, 88, affords sulfisoxazole (98) after removal of the acetyl group. 

A catch and release synthesis of tetrazoles and cyclic amidines has been reported making use of solid-supported oximes [94]. When bound sulpho-nyloximes, obtained by reacting polymer supported sulfonyl chloride with oximes, were reacted with nucleophiles, tetrazoles or cychc amidines were obtained (Scheme 19). Alternatively, the use of TMS-CN affords imino nitriles, which have been used as intermediates for the preparation of indoles, 1,2,3,4-tetrahydropyridines, quinoxalines and benzimidazoles. 

Scheme 19 Synthesis of different heterocycles from resin-bound intermediate sulfonyl-oximes...

A possible extension of the modified Neber reaction would be the synthesis of sulfonyl-substituted 2ff-azirines following the chemistry shown in Scheme 17 [27]. Unexpectedly, the oxime derived from -keto sulfones could not be converted into the oxime tosylate. Therefore, a different route to these requisite starting materials was designed, viz., via the corresponding sulfides 30 which were then oxidized with peracid to the sulfones 31. 

Reactive structures that interfere with the biochemical assay (aldehydes, acyl-halides, sulfonyl-halides, Michael acceptors, epoxides, aziridines, oximes, N-oxides). 

Increasing interest is expressed in diastereoselective addition of organometallic reagents to the ON bond of chiral imines or their derivatives, as well as chiral catalyst-facilitated enantioselective addition of nucleophiles to pro-chiral imines.98 The imines frequently selected for investigation include N-masked imines such as oxime ethers, sulfenimines, and /V-trimcthylsilylimines (150-153). A variety of chiral modifiers, including chiral boron compounds, chiral diols, chiral hydroxy acids, A-sull onyl amino acids, and /V-sulfonyl amido alcohols 141-149, have been evaluated for their efficiency in enantioselective allylboration reactions.680... 

Kinetics and mechanisms of gas-phase pyrolysis of sulfonyl hydrazones and their oxime analogues have been reported for the first time " it is proposed that cyanoarene formation arises in each case via a six-membered transition state (60). The lower limit... 

The approach, which differs from other recent syntheses (3,4,5), is outlined in Scheme 1. Three points may be noted (i) in the Grignard addition to 2,3-0-isopropylidene-D-ribose (2) the D-allo configuration in (3 is in accordance with the Felkin-Anh model (0 and is to be expected from our earlier work (1 ) (ii) methane-sulfonylation of the oxime ( ) serves not only to dehydrate the oxime but to introduce a leaving group for ring closure at the next step (iii) the intramolecular displacement to form the pyrrolidine ring (( ) ] proceeds cleanly and with complete inversion of... 

To explain the difficulties encountered in the reuse of sulfonyl chloride functionalized ionic liquids during Beckmann rearrangement, Deng and colleagues proposed a mechanism for rearrangement of cyclohexanone oxime (equation 97). 

A wide range of organic azides such as alkyl,80 alkenyl,79,100 aryl, including dinitrophenyl and picryl,101-103 heterocyclic,28,91 trimethylsilyl,79,104 acyl,9 phosphoryl,105 sulfonyl,106 alkoxycarbonyl,9 and oxime azides107 has been found to add to norbornene,25,79,90,104,105,107-121 its derivatives,104 106,1 13,120,122-128 or to related bridged bicyclic... 

Benzaldehyde oxime, 2756 Benzanthrone, 3730 Benzeneamine, see Aniline, 2347 Benzene-l,4-bis(diazonium perchlorate), 2153 Benzene-l,3-bis(sulfonyl azide), 2203 (/-Benzenecyclopentadienyliron(II) perchlorate, 3390 f Benzene, 2281... 

Radical chemistry has witnessed remarkable progress since the mid 1980s [1], In addition to common radical C2 synthons such as alkenes and alkynes [2], several radical Cl synthons are also available, including carbon monoxide, isonitriles, and sulfonyl oxime ethers [3, 4]. As featured in Scheme 6.1, a variety of combinations of radical Cl and C2 synthons are now possible, which makes radical methodologies more attractive and permits the design and implementation of a wide range of multicomponent processes. 

Radical C1 synthons CO, isonitrile, sulfonyl oxime ether, etc. Scheme 6.1... 

Sulfonyl oxime ethers function as efficient radical Cl acceptors [45]. The instance in Scheme 6.26, in which a bissulfonyl oxime ether is used as a radical Cl acceptor, showcases the strategic aspect of this unique method for the synthesis of... 

The combination of carbon monoxide with sulfonyl oxime ethers allow for a set of multicomponent coupling reactions involving consecutive Cl/Cl-type coupling, a rare class of radical multicomponent reactions. In Scheme 6.27, examples of three-, four-, and five-component coupling reactions are shown [46], In these reactions, allyltin is not incorporated into the product, but serves as an acceptor of the phenylsulfonyl radical and a source of the tributyltin radical, which delivers the radical chain. 

Very recently it was shown that sulfonyl oximes 359 are suitable reagents for the addition of oxime functions to olefins 355 (entry 22) [403]. This C-C bond-forming reaction proceeded for a wide range of terminal and 1,1-disubstituted substrates with formal Markovnikov selectivity using catalytic amounts of 357a. Branched oximes 360 were isolated in 33-95% yield. 

The reaction between sulfonyl chlorides and cycloalkanone oximes in the presence of pyridine is followed by Beckmann rearrangement to the imidochlorides, which give the corresponding lactim ethers with alcohol.58... 

Di-O-sulfonate oximes were also prepared by the author in the current invention using benzene 1,3-sulfonyl chloride. 

This S,42-type reaction on the oxime sp nitrogen has been found to be quite general. Cyclic imine 79 can for example be prepared by treatment of ( )-0-methylsulfonyl oxime ( )-78 having an intramolecular active methine group with l,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (Scheme 34). In this reaction, anft-O-sulfonyl oxime ( )-78 smoothly converted into cyclic imine 79, while the syn-isomer (Z)-78 did not undergo such cyclization. 

As mentioned previously, the cyclization of phenethyl ketone oximes with [Bu4N]Re04 and CF3SO3H and the cyclic imine formation from 0-sulfonyl oximes both proceed by intramolecular S 2-type reaction on the nitrogen atom of the oximes (Scheme 33). ° In contrast, both of the E- and Z-isomers cyclized smoothly and only 8-hydroxyquinoline was obtained regioselectively without forming 6-hydroxy derivatives. These phenomena are not consistent with a nucleophilic substitution reaction, and the cyclization of 0-2,4-dinitrophenyloxime 80a seemed to proceed by another reaction pathway (Scheme 37). To check isomerization of the 0-2,4-dini-trophenyloxime 84, the Z-isomer was treated with NaH and m-cresol. The isomerization of (Z)-84 hardly occurred, but 4-phenylbutan-2-one azine (85) and 4-phenyl-2-butanone (86) were obtained in 27 and 11%... 

A similar method has been used to synthesize spirocyclic glycosyl diaziridines and diazirines (e.g., 66 and 67), which are used as glycosylidene carbene precursors. The diaziridine is made by reaction of the sulfonylated oxime 65 with ammonia, followed by oxidation to the diazirine with iodine (Scheme 23). 

Tosyloxyimino)-2,2-dimethyl-l,3-dioxane-4,6-dione l,3-Dioxane-4,5,6-trione, 2,2-dimethyl-, 5-0-[(4-methylphenyl)sulfonyl]oxime (9) (215436-24-1)... 

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