A Novel Dimerization of Methyl p-Tolylpropynoate in Fluorosulfonic Acid with Conservation of the Triple Bond

Savechenkov, Pavel Y.; Rudenko, A. P.; Васильев, А. В.

doi:10.1023/b:rujo.0000045207.82756.52

Cited by 11 publications

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“…As follows from the data in Table 5, isomer mixtures IVd, IVe, IVl, IVo-IVq, Vo, and Vp contain mainly the E isomers whose fraction reaches 95%; they result from syn-addition of superacids HSO 3 F and CF 3 Table 5). Isomer mixtures IVe and IVl, which were obtained in HSO 3 F at 0°C, contained the corresponding Z isomers as the major components; presumably, the reason is the presence of an electrondonor methoxy group in the para-position with respect to the double C=C bond, which facilitates isomerization.…”

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“…We recently initiated studies on protonation and subsequent transformations of acetylenic compounds in superacidic media [1][2][3][4][5][6], which opened new prospects in the application of superacids [7] in synthetic organic chemistry. Stang [8,9] and Olah [10] were the first to report on the addition of superacids (HSO 3 F and CF 3 SO 3 H) to alkyl-and dialkylacetylenes with formation of the corresponding vinyl fluorosulfonates and trifluoromethanesulfonates.…”

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“…SO3 H at the triple carbon-carbon bond. The E/Zisomer ratio depends on the temperature: raising theTable 5.…”

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Protonation of 3-Arylpropynoic Acid Derivatives in Superacids

Walspurger¹,

Васильев

Sommer³

et al. 2005

Russ J Org Chem

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According to the 1 H and 13 C NMR data, 3-arylpropynoic acids and their esters XC 6 H n -C C-CO 2 R (R = H, Me, Et) having electron-withdrawing substituents in the benzene ring (X = NO 2 , CN, COMe, CO 2 Me) exist in HSO 3 F at -80 to 0°C as XC 6 H n -C C-C + (OH)OR ions. Derivatives with other substituents (X = H, F, Me, MeO) in HSO 3 F or CF 3 SO 3 H above -40°C undergo protonation at the acetylenic carbon atom neighboring to the acid group to give unstable vinyl-type XC 6 H n -C + =CH-CO 2 R cations which are then transformed into mixtures of stereoisomeric (Z and E) fluorosulfonates or triflluoromethanesulfonates XC 6 H n -CY=CH-CO 2 R (Y = OSO 2 F, OSO 2 CF 3 ), the E isomer prevailing.

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Protonation of 3-Arylpropynoic Acid Derivatives in Superacids

Walspurger¹,

Васильев

Sommer³

et al. 2005

Russ J Org Chem

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“…We recently reported on an unusual low-temperature dimerization of methyl 3-(4-methylphenyl)propynoate (I), which involved intermediate formation of cation A [1]. It seemed reasonable to estimate the scope of the revealed reaction as applied to other acetylene compounds, and (what is the most important) to use the vinyl-like cations generated therefrom by the action of HSO 3 F as addends to foreign organic substrates.…”

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“…The structure of compounds IV and V was determined on the basis of their IR, 1 H and 19 F NMR, and mass spectra with account taken of published data for structurally related compounds [1]. The reaction mixtures were separated by column chromatography on silica gel using a 2-5% solution of ethyl acetate in hexane as eluent.…”

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