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Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
Molybdenum-Promoted Synthesis of Isoquinuclidines with Bridgehead CF3 Groups
Justin H Wilde1, Jacob A Smith1, Diane A Dickie1
1Department of Chemistry , University of Virginia , Charlottesville , Virginia 22904 , United States.
Abstract:
The preparation of the complex MoTp(NO)(DMAP)(4,5-η2-(2-trifluoromethyl)pyridine) (DMAP = 4-(dimethylamino)pyridine; Tp = tris(pyrazolyl)borate) is described. The CF3 substituent is found to preclude κ-N coordination, allowing for direct coordination without protection of the nitrogen. The dihapto-coordinate complex can be isolated as a single diastereomer, methylated, and reacted with a range of nucleophiles. Oxidative decomplexation affords the free dihydropyridines in good yield (75-90%). As a demonstration of synthetic utility, a series of novel bridgehead CF3-substituted isoquinuclidines was prepared from these decomplexed dihydropyridines.
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