Syntheses of (1 R ,2 S ,3 R ,4 S )-1,7,7-trimethyl-2-pyridin-2-ylmethylbicyclo[2.2.1]-heptane-2,3-diol ( 7 ), (1 R ,2 S ,3 R ,4 S )-1,7,7-trimethyl-2-[(6-methyl)-pyridin-2-ylmethyl-bicyclo-[2.2.1]heptane-2,3-diol ( 13 ), and (1 R ,2 S ,2 ’R ,4 R )-1,7,7-trimethyl-2-piperidin-2-ylmethyl-bicyclo[2.2.1]heptan-2-ol ( 19b ) from commercially available ( d )-camphor ( 1 ) are described. Key steps of the syntheses involved substrate-controlled diastereoselective alkylation and platinum oxide-catalyzed hydrogenation reactions. These compounds, and other intermediate amino alcohols in their syntheses, were successfully utilized as ligands in enantioselective diethyl zinc (Et 2 Zn) addition to benzaldehyde with moderate enantioselectivity.
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Calculations Were Conducted Using the MM2 Force-Field in Chem3D Ultra 8.0 Software CS, ChemOffice Chem3D Ultra 8.0, CambridgeSoft, Cambridge.
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