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Alternative dialkyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate Hantzsch esters have been screened for the reduction of substrate 2c: bis-tert-butyl (82:18 e.r.), bisneopentyl (83:17 e.r.), mixed methyl-tert-butyl (85:15 e.r.). The use of alternative substituents in the 2,6 positions of the Hantzsch ester leads to diminished enantioselectivities. Alternative amines that were screened with the TRIP counteranion using 2c as substrate are: pyrrolidine (98:2 e.r.), dibenzylamine (97:3 e.r.), O,N-dimethylhydroxylamine (94:6 e.r.), and methylamine (90:10 e.r.). Other chiral phosphate and carboxylate counteranions have been studied but typically gave lower e.r. values. The full details of the catalyst screen will be reported in due course.
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