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

Sunagatullina, Alisa S.; Lutter, Ferdinand H. und Knochel, Paul (2022): Preparation of Primary and Secondary Dialkylmagnesiums by a Radical I/Mg-Exchange Reaction Using sBu(2)Mg in Toluene. In: Angewandte Chemie International Edition, Vol. 61, No. 13

Abstract

The treatment of primary or secondary alkyl iodides with sBu(2)Mg in toluene (25-40 degrees 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.

• Item Type: Journal article
• Faculties: Chemistry and Pharmacy > Department of Chemistry
• Subjects: 500 Science > 540 Chemistry
• ISSN: 1433-7851
• Language: English
• DFG: Gefördert durch die Deutsche Forschungsgemeinschaft (DFG) - 491502892