Abstract: | It is demonstrated for the first time that the site-selectivity for the Fe+-mediated C? H bond activation of aldimines R1N?CHR2 (R1, R2 = alkyl) involves the alkyl chain R1 by a factor ≥ 12 in comparison to the alkenyl part R2. This finding explains previous observations that dehydrogenation of intermediates formed by alkene loss from either R1 or R2 of R1N?CHR2/Fe+ preferentially involves the alkyl part. |