Diastereoselective couplings of salicylaldehyde, anisaldehyde and 2-pyridylaldehyde with crotyl- and cinnamylindium reagents were studied. The syl/anti selectivity was found to depend largely on the ligands on the indium atom of the allylic indium reagents. A syn-selective cinnamylation of salicylaldehyde was realized by the combination of cinnamyl acetate and indium(I) iodide, whereas an anti-selective coupling with salicylaldehyde was achieved by the indium trichloride/aluminium-mediated cinnamylation.

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Die Benzothjazoline (I) reagieren mit Chloracetylchlorid zu den Amiden (II).

reactions of organo-metal compounds reactions of organo-metal compounds O 0350 -065Indium-Mediated Reaction of 1,3-Dichloro-and 1,3-Dibromopropenes with Carbonyl Compounds. Generation of Novel 3,3-Diindiopropene.-Aromatic aldehydes such as benzaldehyde (I) undergo an indium-mediated reaction with 1,3-dichloropropene (II) to give the syn-chlorohydrin ( III) predominantly. 1,3-Dibromopropene yields under similar conditions the vinyloxirane (VI), the allylic alcohol (VII), and the diol (VIII). The formation of (VII) is believed to involve a unique allylic diindium reagent, 3,3-diindiopropene. -(ARAKI, S.; HIRASHITA, T.; SHIMIZU, H.; YAMAMURA, H.; KAWAI, M.; BUTSUGAN, Y.; Tetrahedron Lett. 37 (1996) 46, 8417-8420; Dep. Appl.

The stereoselective outcome of the title reaction is found to depend not only on the nature of aldehyde, but also on ligands on allylindium intermediates. Configuration of allylic compound and solvent used can also influence the stereoselectivity. -(HIRASHITA*, T.; KAMEI, T.; SATAKE, M.; HORIE, T.; SHIMIZU, H.; ARAKI, S.; Org. Biomol.