Intramolecular C−N Bond Formation Reactions Catalyzed by Ruthenium Porphyrins:  Amidation of Sulfamate Esters and Aziridination of Unsaturated Sulfonamides

Ruthenium porphyrins [Ru(F<sub>20</sub>-TPP)(CO)] (F<sub>20</sub>-TPP = 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato dianion) and [Ru(Por*)(CO)] (Por* = 5,10,15,20-tetrakis[(1<i>S</i>,4<i>R</i>,5<i>R</i>,8<i>S</i>)-1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimethanoanthracen-9-yl]porphyrinato dianion) catalyzed intramolecular amidation of sulfamate esters <i>p</i>-X-C<sub>6</sub>H<sub>4</sub>(CH<sub>2</sub>)<sub>2</sub>OSO<sub>2</sub>NH<sub>2</sub> (X = Cl, Me, MeO), XC<sub>6</sub>H<sub>4</sub>(CH<sub>2</sub>)<sub>3</sub>OSO<sub>2</sub>NH<sub>2</sub> (X = <i>p</i>-F, <i>p</i>-MeO, <i>m</i>-MeO), and Ar(CH<sub>2</sub>)<sub>2</sub>OSO<sub>2</sub>NH<sub>2</sub> (Ar = naphthalen-1-yl, naphthalen-2-yl) with PhI(OAc)<sub>2</sub> to afford the corresponding cyclic sulfamidates in up to 89% yield with up to 100% substrate conversion; up to 88% ee was attained in the asymmetric intramolecular amidation catalyzed by [Ru(Por*)(CO)]. Reaction of [Ru(F<sub>20</sub>-TPP)(CO)] with PhINSO<sub>2</sub>OCH<sub>2</sub>CCl<sub>3</sub> (prepared by treating the sulfamate ester Cl<sub>3</sub>CCH<sub>2</sub>OSO<sub>2</sub>NH<sub>2</sub> with PhI(OAc)<sub>2</sub>) afforded a bis(imido)ruthenium(VI) porphyrin, [Ru<sup>VI</sup>(F<sub>20</sub>-TPP)(NSO<sub>2</sub>OCH<sub>2</sub>CCl<sub>3</sub>)<sub>2</sub>], in 60% yield. A mechanism involving reactive imido ruthenium porphyrin intermediate was proposed for the ruthenium porphyrin-catalyzed intramolecular amidation of sulfamate esters. Complex [Ru(F<sub>20</sub>-TPP)(CO)] is an active catalyst for intramolecular aziridination of unsaturated sulfonamides with PhI(OAc)<sub>2</sub>, producing corresponding bicyclic aziridines in up to 87% yield with up to 100% substrate conversion and high turnover (up to 2014).