The Mn(OAc)-promoted oxidative phosphonylation of N,N-dimethylenaminones with H-phosphonates, involving a chemo- and regioselective C-C bond cleavage and C-P bond formation in one step, provided successfully functionalized β-ketophosphonates under mild reaction conditions. Oxidative C-H/P-H cross-coupling reactions via C-C(C═O) bond cleavage and mechanistic studies are conducted preliminarily, and a possible mechanism is proposed. This novel method proceeds in good to excellent yields, shows operational simplicity, broad substrate scope, and large-scale preparation.
A concise and efficient route for the synthesis of highly substituted imidazopyrroloquinoline derivatives by simply refluxing a reaction mixture of different types of isatins and heterocyclic ketene aminals (HKAs) by acetic acid was developed. This method is suitable for combinatorial and parallel syntheses in drug discovery; consequently, a library of highly substituted imidazopyrroloquinoline derivatives was rapidly constructed using the present protocol.
Divergent cascade syntheses constitute a highly attractive and challenging area in synthetic chemistry, and can exhibit unexpected chemoselectivity. Herein, a Brønsted acid-controlled protocol is described for the efficient catalysis of two different reactions, namely acylation cascade- and [1+2+3]-type cyclization of enaminones and isatins for the concise synthesis of highly functionalized pyrrolo[3,4-c]quinolin-1-ones and spirooxindoles in the presence of carboxylic acids and KHSO4, respectively. The observed chemoselectivity was reasonably explained by trapping the intermediate α,β-unsaturated 2-oxindoles, and the source of the hydroxyl group, carbocation intermediate, and amination reaction were also evaluated.
An
unprecedented method for the construction of thiazole-2-thiones
via an oxidative cascade cyclization strategy is described. The novel
protocol involves the simultaneous formation of two CS bonds
and a CS bond on the structure of enaminones in a single operation
through a cascade of C(sp2)H/C(sp3)H
bond sulfurations and C(sp3)–H bond thiocarbonylation.
This transformation allows for the efficient synthesis of thiazole-2-thiones
with broad tolerance in moderate to excellent yields from simple enaminones
with elemental sulfur.
A direct
Csp3–H bond oxidative thioesterification
of methyl ketones with aromatic thiols/disulfides promoted by TBAI/K2S2O8 has been developed. The reaction
provides successfully a simple and efficient method for the synthesis
of functionalized α-ketothioesters of aromatic thiols. This
practical methodology exhibits readily available starting materials,
large-scale applicability, synthetic application, and broad functional
group tolerance. A possible mechanism for the transformation is proposed.
Enaminones are gaining increasing interest because of their unique properties and their importance in organic synthesis as versatile building blocks. N,N-Dimethyl enaminones offer a better leaving group (a dimethylamine group) than other enaminones, and allow further elaboration via a range of facile chemical transformations. Over the past five years, there have been an increasing number of reports describing the synthetic applications of N,N-dimethyl enaminones. This review provides a comprehensive overview on the synthetic applications of N,N-dimethyl enaminones that have been reported since 2016.1 Introduction2 Direct C(sp2)–H α-Functionalization2.1 Synthesis of α-Sulfenylated N,N-Dimethyl Enaminones2.2 Synthesis of α-Thiocyanated N,N-Dimethyl Enaminones2.3 Synthesis of α-Acyloxylated N,N-Dimethyl Enaminones3 Functionalization Reactions via C=C Double Bond Cleavage3.1 Synthesis of Functionalized Methyl Ketones3.2 Synthesis of α-Ketoamides, α-Ketoesters and 1,2-Diketones3.3 Synthesis of N-Sulfonyl Amidines4 Construction of All-Carbon Aromatic Scaffolds4.1 Synthesis of Benzaldehydes4.2 Synthesis of the Naphthalenes5 Construction of Heterocyclic Scaffolds5.1 Synthesis of Five-Membered Heterocycles5.2 Synthesis of Six-Membered Heterocycles5.3 Synthesis of Quinolines 5.4 Synthesis of Functionalized Chromones5.5 Synthesis of Other Fused Polycyclic Heterocycles6 Conclusions and Perspectives
A novel and facile Cu-catalyzed addition/cyclization cascade of o-cyanoarylacrylamide was developed. The process exhibits significant functional group tolerance, and provides an efficient and straightforward pathway for the synthesis of various phosphonylated quinoline-2,4(1H,3H)-diones.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.