Novel aryne Diels-Alder reactions with functionalized acyclic dienes are reported. These give useful cis-substituted dihydronaphthalene building blocks in good yield which are not easily accessible via other means, as demonstrated in the synthesis of sertraline. The first asymmetric aryne cycloaddition with an acyclic diene is also reported, giving excellent diastereoselectivities with Oppolzer's sultam as a chiral auxiliary.

Palladium-catalyzed allylic substitution is one of the main reactions for testing new chiral ligands. The most relevant examples from the work published in the period 2007 to mid-2010 are reviewed. The vast majority of the work published within this timeframe relies upon the application of chiral ligands for asymmetric induction. The recent advances in the development and applications of new chiral P-P, P-N, P-O, P-S, N-N, N-S, S-S, and NHC ligands are covered and are the main focus of this chapter. Other aspects of enantioselective palladium allylic alkylations are discussed in the subsequent sections, for example, heterogeneous catalysis, the use of chiral salt additives, and recent applications in kinetic resolution.

Palladium-Catalyzed Enantioselective Allylic Substitution -[70 refs.]. -(MILHAU, L.; GUIRY, P. J.; Top. Organomet. Chem. 38 (2011) 95-154 ; Cent. Synth. Chem. Biol., Univ. Coll., Dublin 4, Ire.; Eng.) -Lindner 47-259

Hydrogenated naphthalene derivatives Q 1010Synthesis of Dihydronaphthalenes via Aryne Diels-Alder Reactions: Scope and Diastereoselectivity. -Reactions with electron-withdrawing substituents on the diene generally proceed favorably, but the strongly electron-donating dimethylamino group gives no trace of cycloadduct (IIIf). In addition, the method is successfully extended to the preparation of enantiomerically enriched products (VIII). With Oppolzers sultam excellent diastereoselectivities (>19:1) are obtained. -(DOCKENDORFF, C.; SAHLI, S.; OLSEN, M.; MILHAU, L.; LAUTENS*, M.; J. Am. Chem. Soc. 127 (2005) 43, 15028-15029; Davenport Res. Lab., Dep. Chem., Univ. Toronto, Toronto, Ont. M5S 3H6, Can.; Eng.) -Bartels 08-075

A novel, short synthetic route has been successfully developed for a key precursor of Quinazolinap ligands. The key step is a Friedel-Crafts-type reaction between 2-naphthol and 4-chloroquinazoline, with moderate to quantitative yields recorded. A variation of this reaction allows for the introduction of an amine group on the naphthalene unit.The expansion of the scope of catalytic asymmetric synthesis relies heavily on the design, preparation and evaluation of chiral ligands for transition metal complexes. 1 Chiral P-N ligands have proven over the years to form a synthetically useful class of ligands, 2 in which QUINAP (1) holds a central place. Developed by Brown in 1993, it opened the way to a class of atropisomeric chiral P-N ligands. 3 Today, applications exist in most of the fields of organometallic catalysis (hydroboration, 4 alkyne addition, 5 diboration, 6 and azomethine cycloaddition 7 ). Our group has since then developed our own series of atropisomeric P-N ligands, Quinazolinap (2; Figure 1) which has been successfully applied to the rhodium-catalysed hydroboration of vinylarenes and palladium-catalysed allylic alkylation, with enantiomeric excesses up to 99% in the former application. 8