The selective formation of the 1,4-dihydropyridine isomer of NAD(P)H is mirrored by the selective formation of 1,4-dihydropyridinate ligand−metal complexes in synthetic systems. Here we demonstrate that ligand conjugation can be used to promote selective 1,3-dihydropyridinate formation. This represents an advance toward controlling and tuning the selectivity in dihydropyridinate formation chemistry. The reaction of (I 2 P 2− )Al-(THF)Cl [1; I 2 P = bis(imino)pyridine; THF = tetrahydrofuran] with the one-electron oxidant (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) afforded (I 2 P − )Al(TEMPO)Cl ( 2), which can be reduced with sodium to the twice-reduced ligand complex (I 2 P 2− )Al(TEMPO) (3). Compounds 2 and 3 serve as precursors for high-yielding and selective routes to an aluminumsupported 1,3-dihydropyridinate complex via the reaction of 2 with 3 equiv of potassium metal or the reaction of 3 with KH.
N-alkylation and N-metallation of pyridine are explored herein to understand how metal-ligand complexes can model NAD+ redox chemistry. Syntheses of substituted dipyrazolylpyridine (pz2P) compounds (pz2P)Me+ (1+) and (pz2P)GaCl2+ (2+) are...
A strained, cyclic hydrocarbon comprising a meta‐quaterphenyl‐based arc that is clamped by an alkyne tether was synthesized via Yamamoto coupling of a dichloro precursor. DFT calculations (B3LYP/6‐31G*) indicate that the lowest‐energy ground state adopts a twisted, C2 conformation that bears 19.0 kcal/mol of strain energy. X‐ray crystallographic analysis confirms that, in the solid state, the molecule adopts a twisted structure that is similar to the calculated C2 conformation. Exposure of the ortho‐linked dichloro precursor to Yamamoto conditions generates 9,9′‐bisfluorenylidene in high yield.
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