Optically active, bicyclic ketones were submitted to Friedländer quinoline syntheses with 2-aminobenzaldehyde to yield regioisomeric linear or angular products. When starting from trans-configured ketones, the linear products are the major isomers (ratios ranging from 76:24 to Ͼ98/2). With cis-

Fischer indole synthesis with bicyclic ketones yields regioselectively linear annulated tetracyclic products when starting from ketones with a relative trans configuration. On the other hand, starting materials with a relative cis configuration give exclusively angular annulated indole derivatives. The starting materials were prepared in optically active form in three steps by a sequence of asymmetric Michael reaction, aldol condensation, and catalytic hydrogenation. The last step yields a mixture of cis and trans diastereoisomers which can be separated by column chromatography. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Friedländer reaction of aminobromobenzaldehydes with an optically active decahydroisoquinolone building block gave new octahydropyrido[3,4-b]acridines with quantitative regioselectivity. The products define a platform for combinatorial chemistry. Bromine functions could be reacted further using Suzuki, Heck, Sonogashira, and Buchwald-Hartwig reactions as well as cyanations. The secondary amino function was deprotected and coupled with amino acids and benzoic acid derivatives. A small model library has been prepared.