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Updated: Dec 27, 2025

Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
The Tetraethylphosphorodiamidate (OP(O)(NEt2)2) Directed Metalation Group (DMG). Directed ortho and Lateral
Manlio Alessi1, Jignesh J Patel1, Kristina Zumbansen1
1Department of Chemistry, Queen's University, 90 Bader Lane, Kingston K7L 3N6, ON Canada.
Abstract:
We report on the tetraethylphosphorodiamidate (-OP(O)(NEt2)2) group as an effective directed metalation group (DMG). Lithiation-electrophile quench of 1 provides a general synthesis of ortho-substituted aryl and naphthyl phosphorodiamidates 4-8. We also describe the phospha anionic ortho-Fries (AoF) rearrangement of the phosphorodiamidates 1a,1b → 2 or 3 and its vinylogous counterpart to the ortho-tolyl phosphorodiamidates 5b → 13. Intermolecular competition experiments demonstrate the approximately equal DMG strength of the -OP(O)(NEt2)2 and the most powerful OCONEt2 groups.
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