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Compositae dermatitis in a Danish dermatology department in one year (I). Results of routine patch testing with the sesquiterpene lactone mix supplemented with aimed patch testing with extracts and sesquiterpene lactones of Compositae plants.

To investigate the frequency of Compositae sensitivity, the recently-developed sesquiterpene lactone mix (SL mix) was included in the standard patch test series. Patients with positive reactions to this or patients suspected of having a Compositae allergy were supplementarily tested with a Compositae mix, consisting of ether extracts of 5 European Compositae plants. In the first year, 686 patients were tested with the SL mix and 79 with the Compositae mix. A total of 31 Compositae-sensitive patients (4.5%) were found. The frequency of positive reactions to either of the mixes was equal, but only 17 of 30 patients tested were positive to both mixes. Testing with the individual ingredients of the Compositae mix showed frequent positive patch test reactions to feverfew, followed in order by chamomile, tansy, yarrow and arnica. The reason for this distribution is discussed and the results of standard, photo- and other plant patch tests are presented. The only partial overlap between positive reactions to the mixes emphasizes the necessity of supplementary testing in patients suspected of Compositae allergy, as well as the lack of a reliable single screening agent. Since no cases of active sensitization or irritant reactions were seen, both the SL mix and the Compositae mix may be considered suitable for routine screening of Compositae allergy.

Adult↗

Selectivity in reactions of allyl diazoacetates as a function of catalyst and ring size from gamma-lactones to macrocyclic lactones.

Catalytic reactions of diazoacetates tethered through zero, one, two, and three ethylene glycol units to an allyl group have been investigated for chemoselectivity, diastereoselectivity, and enantioselectivity. Results from cyclopropanation, carbon-hydrogen insertion, and oxonium ylide generation are compared from reactions of achiral and chiral catalysts of copper(I) and dirhodium(II) carboxylates and carboxamidates. Relative to results from intermolecular reactions of ethyl diazoacetate with allyl ethyl ether, intermolecular reactions show a diversity of selectivities including preference for the opposite configurational arrangement from the one preferred in corresponding intermolecular cyclopropanation reactions. Enantioselectivities for cyclopropanation are dependent on the catalyst ligands in a manner that reflects divergent trajectories of the carbon-carbon double bond to the reacting carbene center. Enantioselectivity increases as a function of ring size with chiral copper catalysts, but the reverse occurs with chiral dirhodium(II) carboxamidates. Mechanistic implications, including those related to the conformation of the reacting metal carbene, offer a new dimension to understanding of enantioselectivity in catalytic asymmetric cyclopropanation reactions.

Allyl Compounds↗

Structure of a lactone, 2,4,6-trideoxy-4,6-dimethyl-2-(2-oxopropyl)-7-O- (phenylmethyl)-L-glycero-D-manno-heptono-1,5-lactone 3-(3,5-dinitrobenzoate).

C26H28N2O10, Mr = 528.5, triclinic, P1, a = 9.524 (1), b = 11.8187 (8), c = 12.615 (1) A, alpha = 66.512 (7), beta = 83.321 (9), gamma = 88.758 (8) degrees, V = 1293.0 (4) A3, Dx = 1.357 g cm-3, Z = 2, lambda(Cu K alpha) = 1.54178 A, mu = 8.99 cm-1, F(000) = 556, T = 293 K, final R = 0.039, wR = 0.048 for 2425 reflections with I greater than 3 sigma(I). The tetra-substituted valerolactone ring has a boat conformation and the relative stereochemistries of the three pairs of adjacent substituents are cis-trans-trans.

Lactones↗