Preparation of Primary and Secondary Dialkylmagnesiums by a Radical I/Mg‐Exchange Reaction Using sBu(2)Mg in Toluene

The treatment of primary or secondary alkyl iodides with sBu(2)Mg in toluene (25–40 °C, 2–4 h) provided dialkylmagnesiums that underwent various reactions with aldehydes, ketones, acid chlorides or allylic bromides. 3‐Substituted secondary cyclohexyl iodides led to all‐cis‐3‐cyclohexylmagnesium reagents under these exchange conditions in a highly stereoconvergent manner. Enantiomerically enriched 3‐silyloxy‐substituted secondary alkyl iodides gave after an exchange reaction with sBu(2)Mg stereodefined dialkylmagnesiums that after quenching with various electrophiles furnished various 1,3‐stereodefined products including homo‐aldol products (99 % dr and 98 % ee). Mechanistic studies confirmed a radical pathway for these new iodine/magnesium‐exchange reactions.