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Chromium complexes, electron-transfer reactions carbenes

Narasaka and Sakurai found that chromium carbene complexes, when exposed to a copper(II) reagent, generate acyl radicals by a one-electron oxidation, and these then undergo addition to electron-deficient alkenes (Scheme 4-27) [50J. The resulting copper(I) species reduces the resulting radical to an anion, and subsequent protonation leads to the addition product. This redox type acyl radical transfer reaction works particularly well for aromatic acyl radical systems, for which decarbonylation is not a problem. Related work has also recently appeared [51]. [Pg.110]

Fischer-type carbenes are known as potential carbene transfer reagents to electron-rich and electron-deficient alkenes. Little is known about the chemistry of carbene complexes with silicon substituents at the carbene C-atom, whereas complexes with germanium, tin, or lead have not yet been prepared. The tungsten-carbene complexes 6 react with an excess of ethyl vinyl ether to give l,2-diethoxy-l-(trialkylsilyl)cyclopropanes 7." Only the f-isomers were formed and similar results can be achieved by using the corresponding molybdenum or chromium complexes. On the other hand, no reaction takes place with 2,3-dihydrofuran or ethyl ( )-but-2-enoate. ... [Pg.832]

The intramolecular reaction of pentacarbonyl[phenyl(3-hexenyloxycarbene)]chromium(0), a chromium carbene complex bearing an alkenyloxy substituent, provides 6-ethyl-5-phenyl-2-oxabicyclo[3.1.0]hexane with moderate exo preference19. This example shows that carbene transfer to electronically neutral olefins can proceed nonstereospecifically. [Pg.1061]


See other pages where Chromium complexes, electron-transfer reactions carbenes is mentioned: [Pg.65]    [Pg.67]    [Pg.114]    [Pg.188]    [Pg.1058]    [Pg.241]    [Pg.502]   
See also in sourсe #XX -- [ Pg.5 , Pg.8 ]




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