The iodine-magnesium exchange reaction allows the preparation of polyfunctional aryl, heteroaryl, or alkenyl magnesium reagents at low temperature. These reagents display the typical reactivity of Grignard compounds and undergo various copper-catalyzed reactions such as allylation or 1,4-addition. Using this halogen-metal exchange reaction, it was possible to generate polyfunctional magnesium reagents on the solid phase.
Functionalized iodopyridines bearing either a chloride, ester or nitrile function were converted to the corresponding organomagnesium derivatives at -40 °C or -78 °C by treatment with i-PrMgBr (1.1 equiv, 0.5 h, > 90% yield). The resulting functionalized Grignard reagents react with aldehydes, TosCN directly or with allylic bromides and benzoyl chloride after transmetalation with CuCN leading to polyfunctional pyridines.
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