Abstract The first primary aminocatalytic direct cross-aldol reaction of acetaldehyde is presented. Among the various vicinal diamines screened, the L-tert-leucine derivative 1c in conjunction with (H 4 SiW 12 O 40) 0.25 was identified as the optimal catalyst; good catalytic activity (up to 99% yield in 4 h), and high enantioselectivities (up to 92% ee) were achieved for a range of donors, including aromatic aldehydes and isatin derivatives. Aqueous ...