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In order to quantify the electrophilic reactivities of common Michael acceptors, we measured the kinetics of the reactions of monoacceptor-substituted ethylenes (H2C═CH-Acc, 1) and styrenes (PhCH═CH-Acc, 2) with pyridinium ylides 3, sulfonium ylide 4, and sulfonyl-substituted chloromethyl anion 5. Substitution of the 57 measured second-order rate constants (log k) and the previously reported nucleophile-specific parameters N and sN for 3–5 into the correlation log k = sN(E + N) allowed us to calculate 15 new empirical electrophilicity parameters E for Michael acceptors 1 and 2. The use of the same parameters sN, N, and E for these different types of reactions shows that all reactions proceed via a common rate-determining step, the nucleophilic attack of 3–5 at the Michael acceptors with formation of acyclic intermediates, which subsequently cyclize to give tetrahydroindolizines (stepwise 1,3-dipolar cycloadditions with 3) and cyclopropanes (with 4 and 5), respectively. The electrophilicity parameters E th...

The kinetics of the reactions of maleic anhydride, N-methylmaleimide, fumaronitrile, diethyl fumarate, and diethyl maleate with pyridinium and sulfonium ylides were studied in DMSO at 20 °C. All of the reactions were found to follow a second-order rate law, and can be described by the linear free energy relationship log k2 (20 °C) = sN(N + E), where N and sN are solvent-dependent nucleophile-specific parameters, and E is an electrophile-specific parameter. The electrophilicity parameters E of the investigated acceptor-substituted alkenes were derived from the linear correlations of (log k2)/sN vs. N, and range from –19.8 to –11.1.

Pyridinium salts Py+-CH2-EWG (EWG = CO2Et, CONEt2, CN, COMe, COPh) reacted with Michael acceptors Ar-CH=C(CO2Et)(Acc) (Acc = CO2Et, COMe, SO2Me, CONH2) at ambient temperature in the presence of base to give [3 + 2]-cycloadducts by stepwise [3 + 2]-cycloaddition of the intermediate pyridinium ylides. Treatment of the crude reaction mixtures with 1 equiv. of chloranil and atmospheric oxygen in the presence of sodium hydroxide gave 1-(ethoxycarbonyl)indolizines by dehydrogenation and elimination of the acceptor group (Acc). A good yield of indolizine was also obtained from Py+-CH2CN and iPr-CH=C(CO2Et)2, which indicates that this method is not restricted to aromatic Michael acceptors. Structurally related isoquinolinium salts react with Michael acceptors analogously to give pyrrolo[2,1-a]isoquinolines.

Kinetics of the reactions of pyridinium, isoquinolinium, and quinolinium ylides with diarylcarbenium ions, quinone methides, and arylidene malonates (reference electrophiles) have been studied in dimethylsulfoxide solution by UV-vis spectroscopy. The second-order rate constants (log k2) were found to correlate linearly with the electrophilicities E of the reference electrophiles, as required by the linear free-energy relationship log k(20°C) = sN(N + E) (J. Am. Chem. Soc. 2001, 123, 9500), which allowed us to derive the nucleophile-specific parameters N and sN for these ylides. Pyridinium substitution is found to have a similar effect on the reactivity of carbanionic reaction centers as alkoxycarbonyl substitution. Agreement between the rate constants measured for the 1,3-dipolar cycloadditions of pyridinium, isoquinolinium, and quinolinium ylides with acceptor substituted dipolarophiles (arylidenemalononitrile and substituted chalcone) and those calculated from E, N, and sN shows that the above correlation can also be employed for predicting absolute rate constants of stepwise or highly unsymmetrical concerted cycloadditions. Deviations between calculated and experimental rate constants by a factor of 10(6) were demonstrated to indicate a change of reaction mechanism.