Transfer hydrogenation of representative aryl and heteroaryl dialkylaminomethyl ketones with formic acid–triethylamine, catalyzed by RuCl [(R, R)-TsDPEN](η-p-cymene), produces the corresponding β-dialkylamino alcohols, 97–99% ee, in 50–73% yields. Asymmetric synthesis of (R)-macromerine, 98% ee, the cactus Coryphantha macromeris alkaloid, is also described.