UNIGE document Scientific Article
previous document  unige:82360  next document
add to browser collection

The rhodium(II)-catalyzed aziridination of olefins with {[(4-nitrophenyl)sulfonyl]imino}phenyl-lambda3-iodane

Published in Canadian Journal of Chemistry. 1998, vol. 76, no. 6, p. 738-750
Abstract The aziridination of olefins with {(4-nitrophenylsulfonyl)imino}phenyl-l3-iodane, NsNTIPh (1c), in the presence of [Rh2(OAc)4] proceeds in yields of up to 85% when the olefin is used in large excess. Under optimized conditions, styrene (4a) is aziridinated with 1 equiv. of NsNTIPh (1c) in 64% yield with 2 mol% of catalyst. The aziridines derived from electron-rich olefins undergo ring-opening under the conditions of the aziridination and afford rearrangement products or pyrrolidines. The aziridination is sterospecific with 1,2-dialkyl- and 1,2-arylalkyl-disubstituted olefins, but nonstereospecific with stilbene.The r-value for aziridination of substituted styrenes is –0.61. No ring-opened products are observed upon aziridination of vinylcyclopropanes. In the presence of chiral RhII catalysts, the aziridination is enantioselective, affording an ee of 73% with cis-b-methylstyrene (4k) and Pirrungs [Rh2{(R)-(–)-bnp}4] catalyst. The experimental results are consistent with a one-step mechanism for transfer of the nitrenoid moiety from the catalyst to the olefin.
Keywords AziridinationNitrene transferRhodium catalysis
Full text
(ISO format)
MULLER, Paul, BAUD, Corine, JACQUIER, Yvan Daniel Michel. The rhodium(II)-catalyzed aziridination of olefins with {[(4-nitrophenyl)sulfonyl]imino}phenyl-lambda3-iodane. In: Canadian Journal of Chemistry, 1998, vol. 76, n° 6, p. 738-750. https://archive-ouverte.unige.ch/unige:82360

141 hits

1 download


Deposited on : 2016-04-05

Export document
Format :
Citation style :