Asymmetric baker’s yeast reductions of bridgehead-substituted bicyclo[2.2.2]octane-2,6-dione derivatives followed by conversion into catalytically active BODOLs for the diethylzinc addition to benzaldehyde

Totalsynthese von (+)‐Crotogoudin

“…Die Forschungsgruppen von Mori und Frejd untersuchten die Reduktion von Bicyclo[2.2.2]octan‐2,6‐dion‐Systemen und demonstrierten, dass dabei hervorragende Enantio‐ und Diastereoselektivitäten möglich sind. Substituenten am Brückenkopf zwischen den Ketonen führten zu höherer Selektivität, wobei jedoch nur zwei Beispiele und Seitenketten mit bis zu zwei Kohlenstoffatomen angeführt wurden 11a. 12a,b Erfreulicherweise ist die Methode jedoch auch bei längerkettigen Substituenten anwendbar.…”

1-Aminobicyclo[2.2.2]octane-2-carboxylic Acid and Derivatives As Chiral Constrained Bridged Scaffolds for Foldamers and Chiral Catalysts

“…Bicyclic molecules are less flexible and bulkier than single-ring compounds, and such a strengthened conformational restriction has been successfully used in the optimization of relevant molecules. Some bioactive natural and synthetic products containing a bicyclo[2.2.2]­octane skeleton were reported, , while derivatives of this scaffold were used as templates for organic and asymmetric synthesis. , In the β-amino acid series, bulky bicyclic side chains significantly reduce the accessible range of backbone torsion angles but also strongly influence the spatial orientation of adjacent chemical groups and building blocks. It is noteworthy that bicyclic carbo-bridged scaffolds have been less studied than bicyclic-fused and heterobridged systems.…”