Claisen aromatic amino rearrangement in the series of fluorinated anilines

The effect ofmeta-substituents in the aromatic ring on the route of Claisen rearrangement ofN-(pent-3-en-2-yl)-3-fluoro(or 3-trifluoromethyl, 3,4-difluoro)anilines induced by ZnCl₂ was investigated. The formation of two possibleortho-alkenylated reaction products was observed. The ratio of these isomers depends on the nature of the acid catalyst. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 188–190, January, 1998.     

Claisen amino rearrangement as a method for synthesis of C-cycloalkenylanilines

Conclusions The reaction of 3-chlorocycloalkenes with excess aromatic amine leads to o-(2-cycloalkenyl)-substituted aromatic amines.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2160–2162, September, 1982.     

Quantum chemical study of the mechanism of the Claisen amino rearrangement

Using the LCAO MO method in the MNDO approximation, we have compared the concerted [3, 3]-sigmatropic and stepwise mechanisms for the acid-catalyzed Claisen amino rearrangement. The latter is preferred.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 634–639, March, 1991.     

The diosphenol Claisen rearrangement

Thermal rearrangement of diosphenol allyl ethers provides a method for attachment of an allyl group to hindered carbon centers.     

Claisen rearrangement of sterically hindered N-alkenylindolines

Conclusions Claisen rearrangement of N-(1-methyl-2-butenyl)-2-methyl-2-ethylindoline occurs under mild conditions upon treatment with acids at 20°C. Tricyclic compounds, namely, 6,6-dimethylperhydroeyclopent[g]-2-methyl-2-ethylindoline and 8-methyl-8-ethylpyrrolidino[h, i]-3-methyl-2-ethylindole, were obtained from 7-(1-methyl-2-butenyl)-2-methyl-2-ethylindoline.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 613–618, March, 1987.     

Palladium-catalysed Claisen rearrangement of 6-allyloxypurines

6-Allyloxypurines readily undergo palladium-catalysed Claisen rearrangement under mild conditions affording N ¹-substituted hypoxanthines. In contrast with the previously reported protocol, the Claisen rearrangement can be performed using Pd(PPh₃)₄ or Pd(dba)₂/dppf in dry THF at 60°C. The reaction can accommodate variously substituted allyl fragments to position N ¹ of the hypoxanthine skeleton with high yields. Retention of the double bond configuration during rearrangement was observed.     

Aza-pinacol rearrangement: acid-catalyzed rearrangement of aziridines to imines

A series of di-, tri-, and tetra-substituted N-tosylaziridines [N-(toluene-p-sulfonyl)aziridines] 1, prepared by aziridination of the corresponding alkenes with N-[(tolyl-p-sulfonyl)imino]phenyliodinane (TsN = IPh), was found to undergo a BF3-catalyzed rearrangement (aza-pinacol rearrangement) under mild conditions to give the corresponding N-tosylimines 2 generally in satisfactory yields.     

The acid-catalyzed rearrangement of 1-N-allylindolines

Zinc chloride-catalyzed rearrangement of 1-N-allylindoline and 1-N-(2-methylallyl)indoline proceeds readily in refluxing xylene to give 7-allylindoline and 7-(2-methylallyl)indoline in 73% and 86% yields, respectively. The reaction of 1-N-2-butenylindoline and zinc chloride give rise to the mixture of 7-(1-methylallyl)indoline, 7-(cis- and trans-1-methyl-1-propenyl)indoline, and 7-(trans-2-butenyl)indoline. On the other hand, the similar reaction of 1-N-(3-methyl-2-butenyl)indoline with zinc chloride led to the formation of a mixture of 1,2,5,6-tetrahydro-4,4-dimethyl-4H-pyrrolo[3,2,1-ij]quinoline and 7-(3-methyl-2-butenyl)indoline.     

The Claisen rearrangement in the aminophenol series

Novel compounds, dihydropyranylaminophenols, were synthesized by condensation of 3,4-dibromo-4-methyltetrahydropyran with aminophenols followed by the Claisen rearrangement ofO-andN-substituted products. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 517–520, March, 1999.     

Lewis acid-catalyzed rearrangement of multi-substituted arylvinylidenecyclopropanes

An interesting rearrangement of arylvinylidenecyclopropanes having three substituents at the 1- and 2-positions of the corresponding cyclopropane catalyzed by Lewis acids to give 6aH-benzo[c]fluorine derivatives via a double intramolecular Friedel-Crafts reaction or to give an indene derivative via an intramolecular Friedel-Crafts reaction is described.     

A novel acid-catalyzed rearrangement of cyclobutanols

Under acid-catalysis 7-arylbicyclo[3.2.0]hept-2-en-6-ols rearrange to diarylmethanes and cyclopenteno-annelated polycyclic aromatic hydrocarbons.     

Claisen rearrangement taking place in the mass spectrometer

Conclusions The Claisen rearrangement of bucharaine and of the aldehyde bucharainal takes place under the conditions of mass spectrometry. At low temperatures inversion predominates and at high temperatures the anomalous rearrangement.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 577–583, September–October, 1970.