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Liang JL, Yuan SX, Huang JS, Che CM: Intramolecular C-N bond formation reactions catalyzed by ruthenium porphyrins: amidation of sulfamate esters and aziridination of unsaturated sulfonamides. J Org Chem. 2004 May 28;69(11):3610-9.
Ruthenium porphyrins [Ru (F (20)-TPP)(CO)] (F (20)-TPP = 5,10,15,20-tetrakis (pentafluorophenyl) porphyrinato dianion) and [Ru (Por*)(CO)] (Por = 5,10,15,20-tetrakis [(1S,4R,5R,8S)-1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimeth anoanthracen-9-yl] porphyrinato dianion) catalyzed intramolecular amidation of sulfamate esters p-X-C (6) H (4)(CH (2))(2) OSO (2) NH (2) (X = Cl, Me, MeO), XC (6) H (4)(CH (2))(3) OSO (2) NH (2) (X = p-F, p-MeO, m-MeO), and Ar (CH (2))(2) OSO (2) NH (2) (Ar = naphthalen-1-yl, naphthalen-2-yl) with PhI (OAc)(2) 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 (20)-TPP)(CO)] with PhI [double bond] NSO (2) OCH (2) CCl (3) (prepared by treating the sulfamate ester Cl (3) CCH (2) OSO (2) NH (2) with PhI (OAc)(2)) afforded a bis (imido) ruthenium (VI) porphyrin, [Ru (VI)(F (20)-TPP)(NSO (2) OCH (2) CCl (3))(2)], 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 (20)-TPP)(CO)] is an active catalyst for intramolecular aziridination of unsaturated sulfonamides with PhI (OAc)(2), producing corresponding bicyclic aziridines in up to 87% yield with up to 100% substrate conversion and high turnover (up to 2014). |
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