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The organocatalytic enantioselective formation of vinyl-substituted all-carbon quaternary stereocentersvia nucleophilic vinylic substitution by
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-substituted-
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-cyanoacetates is presented. The reaction proceedswell for different
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-substituted-
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-cyanoacetates and
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-chloroalkenones using a dimeric cinchona alkaloidphase-transfer catalyst giving the products in good yield and with enantioselectivities up to 98% ee.