Allyl sulfamide

In addition, Shi and coworkers demonstrated that the allylic C-H bond of terminal alkenes 1 could be activated by the Pdn complex generated from oxidative addition of Pd° to di-tert-butyldiaziridinone 30 [36]. The subsequent nucleophilic attack at [(re-ally l)Pd complex 33 gives allyl sulfamide 34 and regenerates the Pd° catalyst after reductive elimination. Coordination between 32 and 35 formed 36,... 

Finally, Katsuki and coworkers [271] described an enantioselective Ru-catalyzed domino reaction, which includes a sulfamidation of an aryl allyl sulfide 6/3-111 using the chiral Ru(salen)-complex 6/3-115, followed by a 2,3-sigmatropic rearrangement of the formed 6/3-112 to give N-allyl-N-arylthiotoluenesulfonamides 6/3-113. On hydrolysis, 6/3-113 yielded N-allyltoluenesulfonamides 6/3-114 (Scheme 6/3.33). The enantioselectivity ranged from 78 to 83% ee. 

Scheme 22 Allylic amination via [2,3]-sigmatropic rearrangement of 2-alkenyl sulfamid-ines...

The proposed chair like transition state for the a branched sulfamate mini mizes gauche interactions betvt een substituents and lead to the syn diaste reoisomer. In the case of the sulfamide oxidation, the preference for the anti isomer may be rationalized as a minimization of allylic 1,3 strain. 

Together with t-BuOOAc the sulfamidation at a benzylic or allylic position in moderate yields by PhS02NHR is mediated by Cu(OTf)2 - 1,10-phenanthroline, Adamantane is also functionalized at C-1 by this method. 

The synthesis of the benzo analogue (34 R = H), 3,2,4-benzothiadiazepine derivative, has also been achieved by the reaction of o-xylylenediamine with sulfamide or sulfonyl chloride <76IJC766, 74MU4>. The dialkylation of the sodium salts of (34 R = H) with alkyl halides gives the corresponding dialkyl derivatives (34 R = Me, Bn or allyl), several of which can be prepared directly from o-xylylenediamine by treatment with 7V,7V -dialkylsulfamides (Equation (5)). 

Other acidic N-nucleophiles successfully allylated by carbonates include synthetic equivalents of ammonia,f f f hydroxylanune, " and hydrazine, cyananude, diarylamines, sulfamide, arenesulfonamides f (see also Scheme 33 ), a glutarinude derivative, trimethylsilyl azide, " and amino esters activated at the nitrogen atom with an electron-withdrawing group. ... 

The elaborate cobalt(II)-porphyrin catalyst [Co(Pl)] further enabled intramolecular amination of C(sp )-H bonds in simple alkyl chains, adjacent to electron-withdrawing groups, or at the allylic or propargylic positions through decomposition of sulfamoyl azide (Scheme 10.21) [50]. Thus, the catalyst promotes nitrene insertion into such C(sp )-H bonds located at the y-position of the sulfamoyl group to afford six-membered cyclic sulfamides in excellent yields, which serve as versatile 1,3-diamine scaffolds. On the basis of mechanistic experiments, a mechanism that is distinct from related Rh -catalyzed C-H amination was proposed. Thus, the 15-electron metalloradical catalyst [Co(Pl)j decomposes the sulfamoyl azide to form a Co -radical nitrene species, which... 

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