Journal ArticleDOI
Regioselective synthesis of heterocycles containing nitrogen neighboring an aromatic ring by reductive ring expansion using diisobutylaluminum hydride and studies on the reaction mechanism
TLDR
It was found that the more electron-rich group migrated preferentially to give the corresponding secondary amines in the reductive ring-expansion reaction of cyclic ketoximes fused to aromatic rings with diisobutylaluminum hydride.Abstract:
A systematic investigation of the reductive ring-expansion reaction of cyclic ketoximes fused to aromatic rings with diisobutylaluminum hydride (DIBALH) is described. This reaction regioselectively afforded a variety of five- to eight-membered bicyclic heterocycles or tricyclic heterocycles containing nitrogen neighboring an aromatic ring, including indoline, 1,2,3,4,5,6-hexahydrobenz[b]azocine, 3,4-dihydro-2H-benzo[b][1,4]oxazine, 2,3,4,5-tetrahydrobenzo[b][1,4]thiazepine, 1,2,3,4,5,6-hexahydroazepino[3,2-b]indole, 2,3,4,5-tetrahydro-1H-benzothieno[2,3-b]azepine, 2,3,4,5-tetrahydro-1H-benzothieno[3,2-b]azepine, 5,6-dihydrophenanthridine, and 5,6,11,12-tetrahydrodibenz[b, f]azocine. The reaction mechanism leading to the rearrangement was investigated on the basis of the restricted Becke three-parameter plus Lee−Yang−Parr (B3LYP) density functional theory (DFT) with the 6-31G (d) basis set. It was found that the reaction proceeds through a three-centered transition state via a stepwise mechanism because th...read more
Citations
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Palladium-Catalyzed C(sp3)-H Oxygenation via Electrochemical Oxidation.
TL;DR: This work reports an electrochemical strategy that takes advantage of anodic oxidation of PdII to induce selective C-O reductive elimination with a variety of oxyanion coupling partners.
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Mild rhodium(III)-catalyzed cyclization of amides with α,β-unsaturated aldehydes and ketones to azepinones: application to the synthesis of the homoprotoberberine framework.
TL;DR: A novel synthesis of azepinone derivatives by using a Rh-catalyzed intramolecular annulation reaction of N-substituted benzamides and α,β-unsaturated aldehydes and ketones is developed.
Journal ArticleDOI
Strain-promoted "click" modification of a mesoporous metal-organic framework.
TL;DR: This new method was used to introduce various functional groups into the MOF mesopores, including succinimidyl ester bioconjugation moieties that allow for straightforward coupling of biomolecules to the pore walls.
Journal ArticleDOI
Enantioselective cyanation via radical-mediated C-C single bond cleavage for synthesis of chiral dinitriles.
TL;DR: The authors present the facile synthesis of chiral 1,5- and 1,6-dinitriles via the radical-mediated ring-opening and enantioselective cyanation of cycloketone oxime esters.
Journal ArticleDOI
A Bis(phosphaethenyl)pyridine Complex of Iridium(I): Synthesis and Catalytic Application to N-Alkylation of Amines with Alcohols
TL;DR: The iridium(I) complex [IrCl(BPEP-H)] (1), coordinated with 2,6-bis[2-(2,4, 6-tri-tert-butylphenyl)-2-phosphaethenyl]pyridine (BPEP) as a PNP-pincer-type phosphaalkene ligand, has been synthesized and fully characterized by elemental analysis, NMR spectroscopy, and X-ray diffraction analysis as discussed by the authors.
References
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A new integral equation formalism for the polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics
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Reaction Path Following in Mass-Weighted Internal Coordinates
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Journal ArticleDOI
New developments in the polarizable continuum model for quantum mechanical and classical calculations on molecules in solution
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