First Example of 1,3-Dipolar Cycloaddition of Carbonyl Ylides to Cyclopropenes

Carbonyl ylide generated from 1-diazo-5-phenylpentane-2,5-dione in the presence of Rh₂(OAc)₄ reacts with 3-substituted cyclopropenes following the 1,3-dipolar cycloaddition pattern to afford substituted 9-oxatricyclo[3.3.1.0^2,4]nonan-6-ones.     

Photochemistry of Isothiocoumarin (= 1H-[2]benzothiopyran-1-one)

Irradiation (λ = 350 nm) of 1H-[2]benzothiopyran-1-one ( 2 ) in the solid state affords selectively and in good yield 6aα, 6bα, 12bα, 12cα -tetrahydrocyclobuta[1, 2-c:4, 3-c′]bis([2]benzothiopyran)-5, 8-dione ( 3 ), the head-to-head (HH) cis-cisoid-cis-cyclodimer of 2 , X-Ray analysis of 2 confirms that this reaction proceeds according to the well-established topochemical principles. The same dimer 3 is obtained in low yields on irradiation of 10⁻¹ M solutions of 2 in either MeOH or MeCN, while no conversion at all is observed in benzene. On irradiation of 2 in MeCN in the presence of tetrachloroethene, the [2 + 2] photocycloadduct 4 is formed in good yield, the conversion 2 → 4 being efficiently quenched by naphthalene. In contrast, no reaction is observed -on irradiation of 2 in the presence of 2, 3-dimethylbut-2-ene, neither in polar nor in apolar solvents.     

1,3-dipolar cycloaddition of fluorinated azomethine ylides at the C=N bond

Azomethine ylides generated by reaction of difluorocarbene with N-alkyl- and N-arylimines derived from benzaldehyde and benzophenone react with N-benzylidenebenzenesulfonamide in a regioselective fashion, yielding the corresponding imidazolidin-4-ones via 1,3-dipolar cycloaddition at the C=N bond. Ylides generated from benzaldehyde imines give rise to mixtures of stereoisomeric 2,5-diphenyl-1-(phenylsulfonyl)-imidazolidin-4-ones, the cis isomer prevailing.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 10, 2004, pp. 1542–1548.Original Russian Text Copyright © 2004 by Novikov, Khlebnikov, Egarmin, Kopf, Kostikov.