Patai S., Rappoport Z. 1997 The chemistry of functional groups. The chemistry of dienes and polyenes. V. 1 / 0869 887

C. Spectroscopic Identification of Allenyl Cations

Substituted allenyl cations 47 have been generated from propargyl alcohols 48 under stable carbocation conditions (SbF5/FSO3H in SO2ClF) (equation 17). On the basis of 13C-NMR chemical shifts, the positive charge has been found to be extensively delocalized with the mesomeric allenyl cations contributing highly to the total ion structure36,37.

13C-NMR spectroscopic studies on ˛-substituted tris(ethynyl)methyl cations 49 prepared from alcohols 50 (equation 18) provided evidence for the participation of resonance structures with allenyl cationic character38. The parent tris(ethenyl)methyl cation (49, R D H) cannot be generated under stable carbocation conditions (SbF5/FSO3H) presumably due to the highly reactive unsubstituted termini of the three ethynyl groups and the resulting low kinetic stability. The chemical shift data (Table 1) give evidence that in all cases C˛ and C are deshielded more than Cˇ (relative to their precursor alcohols).

Recently, the 13C-NMR spectrum of 1-mesityl-3,3-dimethylallenyl cation (51) generated from the propargyl alcohol was measured (equation 19)39. The cation exhibits strong shielding for the CC -atom (192 ppm).

III. BUTATRIENYL CATIONS

The homologue of allenyl cation, butatrienyl cation 53 is the mesomeric form of ˛-ethynyl stabilized vinyl cation 52. Such a species was generated for the first time by Kobayashi, Sonoda and Taniguchi in 197740, by the solvolysis of the butatrienyl halides 54a and 54b in aqueous ethanol. The first-order kinetics, the leaving-group effect (kBr/kCl D 52) and the Grunwald Winstein’s m value of ca 0.5 show that 54a and 54b solvolyze by an SN 1 mechanism with the mesomeric butatrienyl cation 55 as the intermediate.

Both the butatrienyl halides 54a and 54b gave the alkyne (56) as the sole product in 97 100% yield41. The kinetics described above fit the mechanistic sequence shown in equation 20 for the formation of the product 56. The mesomeric butatrienyl vinyl cation 55

An Me

O+

C C

O

o-An

An

O

C C

O

o-An

(56)

If one compares the solvolyses of 2-bromo-1,1-diphenyl-4-(p-methoxyphenyl)-but-1- en-3-yne (57) and 4,4-diphenyl-1-bromo-1-(p-methoxyphenyl)-buta-1,2,3-trienes (58, X D Br) in aqueous ethanol (equation 21), the destabilization of the intermediate cation 59 by the large inductive effect of the triple bond as compared to its conjugative effect is evident42. Only in the case of 58 could the substitution product butatrienyl enol ether 60 be isolated in 40% yield, while it was only detected by UV and IR spectroscopy in the solvolysis product of 57. The faster observed reaction rate of 58 as compared to 57 was ascribed to a difference in their ground-state energies42.

Butatrienyl cations 61 were also implied in the solvolysis of the ˛-propynyl vinyl triflate 6243. The vinyl triflate solvolyzes 35 70 times faster than the corresponding simple vinyl analogues and gives products resulting mainly from the ˛-alkynyl vinyl cation 63. A small amount of the allenic ketone 64 derived from the butatrienyl cation is also detected (equation 22).

An allenyl cation 65 is involved as an intermediate in the room-temperature isomerization of 1-chloro-1,4,4-tris(4-methylphenylthio)butatriene (66) to the tris(4- methylphenylthio)butenyne (67)43 (equation 23).

RS Cl

C C

RS C

C

SR

(67)

Higher homologues than the butatrienyl cations are not known to the best of my knowledge. The summary given here provides strong evidence for the existence of the cumulated vinyl cations, i.e. allenyl and butatrienyl cations. A leap into the preparatory domain, harvesting the potentials of these cations, should definitely be a fruitful venture.

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