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Regiodivergent Metalation of Pyridines Using Mixed Ti-TMP and Ti-Fe-TMP Amides at Room Temperature
Xiao-Di Ma1, Jun-Ting Li1, Jing-Yan Kong1
1College of Chemistry, Beijing Normal University, Beijing 100875, China.
Abstract:
We have developed two mixed-metal TMP amides (TMP = 2,2,6,6-tetramethylpiperidyl), Ti-1·2(TMPMgCl·LiCl) and Ti-1·FeCl2·2(TMPMgCl·LiCl), to enable the rapid metalation of various unactivated and functionalized pyridines with high functional group tolerance and regioselectivity at room temperature. These novel organometallic reagents demonstrate unprecedented regiodivergence: Ti-1·2(TMPMgCl·LiCl) selectively metalates 2- or 3-functionalized pyridines at the C6 position, while Ti-1·FeCl2·2(TMPMgCl·LiCl) promotes the metalations ortho to the functional groups.
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