Low-valent manganese generated by the reduction of manganese(II) chloride using lithium naphthalenide (Rieke manganese) promotes reactions of alkyl halides with electrophiles such as acyl chloride, aldehyde, and ketone to afford alkylation products. N-Haloalkyl-N-allyltosylamides are converted to pyrrolidine and piperidine derivatives in high yields. In the reactions of aromatic aldehyde and ketone, pinacol-type coupling products are produced.