Aliphatic imines take center stage: The first enantioselective catalytic addition of arylboronic acids to branched and unbranched N-tosyl- and N-diphenylphosphinoyl aliphatic imines has been developed with selectivities of up to 98 % ee (see scheme; acac=acetylacetonate, coe=cyclooctene, (R,R)-deguphos=(R,R)-1-benzyl-3,4-bis(diphenylphosphino)pyrrolidine).