Metal-catalyzed carbenoid reactions with iodonium and sulfonium ylides

✍ Scribed by Paul Müller; Daniel Fernandez; Patrice Nury; Jean-Claude Rossier

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: English
• Weight: 291 KB
• Volume: 11
• Category: Article
• ISSN: 0894-3230
• DOI: 10.1002/(sici)1099-1395(199805)11:5<321::aid-poc6>3.0.co;2-#

✦ Synopsis

Transition metal-catalyzed decomposition of phenyliodonium and diphenylsulfonium ylides was investigated with regard to application in asymmetric carbenoid reactions. Phenyliodonium ylides react in the presence of Rh(II) catalysts with the same selectivity in inter-and intramolecular cyclopropanations as the corresponding diazo compounds, and intramolecular CH insertions proceed with identical enantioselectivities. With diphenylsulfonium ethoxycarbonylmethylide the Cu(I)-catalyzed cyclopropanation of olefins affords trans/cis ratios and asymmetric inductions identical with those of diazo compounds, but with Rh(II) catalysts some small, although significant, selectivity variations occur, which are ascribed to coordination of diphenyl sulfide to one of the coordination sites of the catalyst.