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Alkenes, substituent effects with carbene addition

Similar correlations of orbital interactions with substituent effects were also found in additions of alkenes to substituted carbenes and of N2 to transition metal complexes (see Zollinger, 1983 b, 1990). [Pg.183]

Despite the dominance of entropy in these reactive carbene addition reactions a kind of defacto enthalpic control operates the entropies of activation are all very similar, so that in any comparison of the reactivities of alkene pairs (i.e., rgi), the rate constant ratios reflect differences in AAHi, which ultimately appear in AAGf Thus carbenic philicity, which is the pattern created by carbenic reactivity, behaves in accord with our qualitative ideas about structure/reactivity relations, as modulated by substituent effects in both the carbene and alkene partners of the addition reactions. [66,99]... [Pg.88]

Supercritical carbon dioxide with a minute co-solvent addition is an effective medium for the 1,3-dipolar cycloaddition of azomethine ylides with DMAD to produce substituted pyrroles.67 The 1,3-dipolar cycloaddition of nitrile ylides [e.g. benzonitrile (4-nitrobenzylide) and 4-nitrobenzonitrile(benzylide)] with acrylamides provided a synthesis of 3,4-dihydro-2//-pyrroles with moderate to good yields.68 The Pt(II)-or Au(III)-catalysed 3 + 2-cycloaddition of the transition metal-containing azomethine ylide (63) with electron-rich alkenes provided a carbene complex (64), which yields tricyclic indoles (65) having a substituent at 3-position (Scheme 17).69 The 1,3-dipolar cycloadditions of azomethine ylides with aryl vinyl sulfones are catalysed by Cu(MeCN)4C104-Taniaphos with nearly complete exo- selectivity and enantioselec-tivities up to 85% ee.10 The 3 + 2-cycloaddition of benzol/>]thiophene 1,1-dioxide... [Pg.392]

Silicon and germanium also exhibit carbene-like chemistry. A review comparing carbene and silylene chemistry was published. All the examples of germylene chemistry are from theoretical studies of their structure and their interaction with alkenes. A practical demonstration of silylene chemistry was reported. Ab initio calculations have been performed on the addition of silylenes to alkenes and they shed new light on the presence of intermediates, the structure of the transition state and the effect of substituents. ... [Pg.278]


See other pages where Alkenes, substituent effects with carbene addition is mentioned: [Pg.59]    [Pg.110]    [Pg.341]    [Pg.530]    [Pg.194]    [Pg.427]    [Pg.405]    [Pg.397]    [Pg.94]    [Pg.186]    [Pg.158]    [Pg.27]   
See also in sourсe #XX -- [ Pg.1207 ]




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Addition carbenes

Additive effects substituents

Alkene, substituent effects

Alkenes carbene addition

Alkenes carbenes

Alkenes carbenes addition

Alkenes effect

Carbene addition

Carbenes addition with

Carbenes substituents

Substituent effects additivity

With Carbenes

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