Allylic sulfonamide

Flowever, Mansuy el al. reported that treatment of olefins with [A-(p-toluenesulfonyl)imino]-phenyliodinane, PhI=NTs, in the presence of a Mn or Fe porphyrin, provided the corresponding aziridine or allylic sulfonamide, depending on the substrate and the catalyst used (Scheme 33).145-147 The reaction has been considered to proceed through a metal-A-toluenesulfonylnitrenoid species. Similarly to epoxidation via the oxo-Mn species, this aziridination is nonstereospecific, and the participation of a radical intermediate has been suggested.146... 

Primary ally lie amines1 In the presence of this catalyst, allylic chlorides or acetates react with sodium p-toluenesulfonamide in THF/DMSO (80 20) to form the corresponding allylic sulfonamide in 60-85% yield. The products are converted into primary allylic amines on reductive cleavage (sodium naphthalenide). 

This mild rearrangement process was found to be general for both secondary 16896 and primary 17079 sulfoximines and in each case the reactions were completely regioselective and gave the primary allylic sulfonamide 172. The overall yields ranged from 79 to 95% and the reactions were found to be compatible with other functional groups (e.g., hydroxy and carbonyl groups). 

Allyl lactone 28, allyl acetate 30, and allyl carbonate 19e give rise to the A-allylated sulfonamides 2935, 3135, and 3236, respectively, as the only product isomers. 

PhMe2Si ethers, sulfonamides, allyl sulfonamides sulfonyl amides, benzyl amides and some esters are also cleaved. ... 

Sultams can also be accessed by intramolecular cyclization of compounds containing preformed C-S-N-C-C fragments with a C-C bond formation as demonstrated in a one-pot synthesis of tricyclic sultam 236 <05SL577>. Tetrahydropyridine 235, obtained from 77,7/-bis(allyl)sulfonamide 234 by ring-closure-metathesis (RCM) followed by isomerization, undergoes radical cyclization in the presence of tris(trimethylsilyl)silane (TTMSS) to give tricycle sultam 236. 

Note that sulfonyl azides and azidoformate esters form N-allyl sulfonamides and carbamates, respectively, in the free-radical reactions (using Ph3SnCH2CH=CH2 as the allyl donor)."]... 

Allylamines An ene-type reaction between the reagent NsN=Se=NNs (prepared from NsNHNa, NsNCIj, and Se) and an alkene at room temperature gives the allylic sulfonamide. Under similar conditions, 1,3-dienes afford l,2-diamino-3-alkenes. 

In nearly simultaneous publications. Mori <01OL1913> and P.A. Evans <01OL3269> disclosed procedures for the enantiospccific allylic amination of A-(arylsulfonyl)anilines providing allylic sulfonamides which could be converted to indolines. In the former approach, palladium-catalyzed cyclization of the allylic sulfonamides 105 led to a mixture of the corresponding indolines 106 and 107. Mori then utilized this type of indolization process in total syntheses of the Strychnos alkaloids (-)-dchydrotubifoline and (-)-tubifolinc. 

Several other types of domino reactions have been employed in the synthesis of natural products. Diastereoselective conversion of allylic carbonate 173 into enone 174 was one key transformation in a total synthesis of (+)-3-isorauniticine 175 (Scheme 27).Treatment of allylic sulfonamide 173 with a palladium catalyst re-gioselectively forms a 7r-allylpalladium intermediate by carbonate displacement. Carbopalladation of the pendant alkene, carbonylation, a second intramolecular alkene insertion, and /3-hydride elimination delivers a 67 22 11 mixture of stereoisomers of which enone 174 is the major product (isolated in 45-53% yield). Carbopalladation products can also undergo anion capture reactions. For instance, during the synthesis... 

Tang et al. described the enantioselective bromoesterification of allylic sulfonamides with NBS as bromine source and benzoic acid as nucleophile, catalysed by (DHQD)2PHAL in combination with (-l-)-camphorsulfonic acid additive. Unfunctionalised olefins were also used as substrates with... 

The similar addition to allenic tosyl sulfonamides produced the hromo allylic sulfonamides which were cyclized with potassium carhonate in DMF (eq 10). ... 

Further examples of allyl substrates that proceed via a symmetrical intermediate include the allyl carbonate 161, which reacts with allyl sulfonamide 163 to give the product 164. Elaboration of compound 164 afforded the natural product mesembrane 165. Related strategies have been used in the synthesis of a range of other natural products. ... 

The synthesis of allyl sulfonamides by imidation of allyl sulfides with chloramine-T (TsNClNa) and subsequent [2,3]-sigmatropic rearrangement has been reported (Scheme 43). ... 

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