RESUMEN
Functionalized arenes and arenols have diverse applications in chemical synthesis and material chemistry. Selective functionalization of arenols is a topic of prime interest. In particular, direct alkylation of arenols using alcohols is a challenging task. In this report, a ruthenium pincer catalyzed direct α-alkylation of ß-naphthol using primary alcohols as alkylating reagents is reported. Notably, aryl and heteroaryl methanols and linear and branched aliphatic alcohols underwent selective alkylation reactions, in which water is the only byproduct. Notably, catalytically derived α-alkyl-ß-naphthol products displayed high absorbance, emissive properties, and quantum yields (up to 93.2 %). Dearomative bromination on α-alkyl-ß-naphthol is demonstrated as a synthetic application. Mechanistic studies indicate that the reaction involves an aldehyde intermediate. DFT studies support this finding and further reveal that a stoichiometric amount of base is required to make the aldol condensation as well as elementary steps required for regeneration of catalytically active species. In situ-generated water molecule from the aldol condensation reaction plays an important role in the regeneration of an active catalyst.
RESUMEN
Metallogels formed from supramolecular interactions of low-molecular-weight gelators (LMWGs) combine the qualities of heterogeneous catalysts and offer the advantages of multifunctionality owing to the facile installation of desired task-specific moieties on the surface and along the channels of the gels. We discuss the applications of a triazole-based Ni(II) gel-derived xerogel (NiXero) having a high density of Ni(II)-nodes and appended primary amines as a recyclable heterogeneous catalyst for Knoevenagel condensation of aldehyde and malononitrile in water and the solvent-free cycloaddition of CO2 to form a series of cyclic carbonates with near-quantitative conversion of the respective epoxides, with low catalyst loading (0.59 mol %), high catalyst stability, and recyclability. The structural advantages of NiXero, due to the concurrent presence of bifunctional Lewis acid-base sites on the channels, open Ni(II) nodes, Ntriazole, pendant -NH2 and its chemical stability, are conducive to the cooperative heterogeneous catalytic activity under mild conditions. This work emphasizes the effective amalgamation of metals with purpose-built ligand systems for the construction of metallogels and their utility as heterogeneous catalysts for desired organic transformations.
RESUMEN
Isoquinoline-enrooted organic small-molecules represent a challenging molecular target in the organic synthesis arsenal attributed to their structural diversity and therapeutic importance. Into the bargain, isoquinolines are significant structural frameworks in modern medicinal chemistry and drug development. Consequently, synthetic organic and medicinal chemists have been intensely interested in efficient synthetic tactics for the sustainable construction of isoquinoline frameworks and their derivatives in enantiopure or racemic forms. This review accentuates an overview of the literature on the modern synthetic approaches exploited in synthesising isoquinolines and their core embedded heterocyclic skeletons from 2021 to 2022. In detail, the methodologies and inspected pharmacological studies for the array of diversely functionalized isoquinolines or their core-embedded heterocyclic/carbocyclic structures involving the introduction of substituents at C-1, C-3, and C-4 carbon and N-2 atom, bond constructions at the C1-N2 atom and C3-N2 atom, and structural scaffolding within isoquinoline compounds have been reviewed. This intensive study highlights the need for and relevance of relatively unexplored bioisosterism employing isoquinoline-based small-molecules in drug design.