An expeditious synthesis of hexahydrobenzo[f]isochromenes and of hexahydrobenzo[f]isoquinoline via iodine-catalyzed Prins and aza-Prins cyclization

Homoallylic alcohols (primary, secondary, or tertiary containing an endocyclic or an exocyclic double bond) react with equimolar amounts of aldehydes (aliphatic or aromatic) and ketones (aliphatic) in the presence of 5 mol % of iodine. This Prins cyclization was used in the preparation of hexahydrobenzo[f]isochromenes and of a 4-hydroxy-tetrahydropyran, in 54-81% yield. The procedure is also efficient for an aza-Prins cyclization of a homoallylic sulfonamide and benzaldehyde, producing a hexahydrobenzo[f]isoquinoline. (C) 2009 Elsevier Ltd. All rights reserved.

SYNTHESIS AND RETRO AZA DIELS-ALDER REACTION OF SOME NEW ISOQUINUCLIDINE DERIVATIVES

N-Benzyl- and N-(alpha-methoxycarbonylethyl)-2,4,6-triphenyl-1,2-dihydropyridines were submitted to Diels-Alder reactions with maleic anhydride or N-phenylmaleimide yielding, diastereoselectively, the corresponding endo-anti adducts. These novel isoquinuclidines showed to be resistant to N-alkylation or N-protonation, undergoing an unexpected fragmentation via a retro aza Diels-Alder process.

Chemically tagging the Hyades stream: does it partly originate from the Hyades cluster?

The Hyades stream has long been thought to be a dispersed vestige of the Hyades cluster. However, recent analyses of the parallax distribution, of the mass function, and of the action-space distribution of stream stars have shown it to be rather composed of orbits trapped at a resonance of a density disturbance. This resonant scenario should leave a clearly different signature in the element abundances of stream stars than the dispersed cluster scenario, since the Hyades cluster is chemically homogeneous. Here, we study the metallicity as well as the element abundances of Li, Na, Mg, Fe, Zr, Ba, La, Ce, Nd and Eu for a random sample of stars belonging to the Hyades stream, and compare them with those of stars from the Hyades cluster. From this analysis: (i) we independently confirm that the Hyades stream cannot be solely composed of stars originating in the Hyades cluster; (ii) we show that some stars (namely 2/21) from the Hyades stream nevertheless have abundances compatible with an origin in the cluster; (iii) we emphasize that the use of Li as a chemical tag of the cluster origin of main-sequence stars is very efficient in the range 5500 K <= T(eff) <= 6200 K, since the Li sequence in the Hyades cluster is very tight, while at the same time spanning a large abundance range; (iv) we show that, while this evaporated population has a metallicity excess of similar to 0.2 dex with respect to the local thin-disc population, identical to that of the Hyades cluster, the remainder of the Hyades stream population has still a metallicity excess of similar to 0.06-0.15 dex, consistent with an origin in the inner Galaxy and (v) we show that the Hyades stream can be interpreted as an inner 4:1 resonance of the spiral pattern: this then also reproduces an orbital family compatible with the Sirius stream, and places the origin of the Hyades stream up to 1 kpc inwards from the solar radius, which might explain the observed metallicity excess of the stream population.