Journal of Organic Chemistry最新文献

Phochrodines A, B, and C have been synthesized using a CH-activation protocol and palladium-catalyzed carbonylation. To avoid issues of regioselectivity, the inherent symmetry of a common intermediate was exploited.

The chemoenzymatic dynamic kinetic resolution of 2-(quinolin-8-yl)benzylalcohols using a combination of lipases and ruthenium catalysts is described. While CalB lipase performs highly selective enzymatic kinetic resolution, the combination with Shvo′s or Bäckvall’s catalysts promotes atropisomerization of the substrate via the reversible formation of configurationally labile aldehydes, thereby enabling a dynamic kinetic resolution. This synergistic approach was applied to the synthesis of a variety of heterobiaryl acetates in excellent yields and enantioselectivities.

Perfluoroalkyl alkenyl iodides (PFAIs) are emerging as highly reactive, storage-stable, and multifunctional fluoroalkyl-bearing reagents, facilitating the manufacture of value-added organofluorides through multi-halo-functionalization. Herein, we developed a water-involved 1,3-aminoxylation of PFAIs with sulfonamides for the chemo-, regio-, and Z-stereoselective synthesis of valuable β-fluoroacyl vinylamines. This reaction proceeded via a sequential deiodoamination and defluoroxylation process under transition-metal-free conditions, featuring a broad substrate scope and good functional group tolerance. Compared to reported methods, some drawbacks, such as multistep manipulation, harsh reaction conditions, the need for expensive catalysts, and the use of toxic/sensitive reagents, could be eliminated. Furthermore, the synthetic potential of this method was demonstrated through scale-up synthesis, postfunctionalization of complex molecules, and ready transformation of the products.

Carbohydrates constitute an important class of biologically relevant natural products. Among the synthetic glycomimetics, C-glycosides are particularly interesting due to their chemical and metabolic stability toward acidic and enzymatic hydrolysis at the anomeric position. The stereochemical outcomes of traditional methodologies to access C-glycosides rely heavily on substrate control. Herein, we report a novel synthetic strategy to access diverse C-glycosides with precise stereochemical control at the anomeric position via formal functional group deletion, where both α- and β-anomers of furanoses and pyranoses can be obtained as single stereoisomers. Additionally, the broad scope of heterocyclic C-glycosides obtained via this strategy further illustrates its potential for empowering future application in both chemical biology research and drug discovery.

An unprecedented approach involving radical-mediated sulfonylation/dearomative ipso-annulation of N-(methyl-2-phenylacetate)propiolamides using arylsulfonyl radical, generated from aryl diazonium salt in the presence of DABSO, is developed. This strategy provides uniquely substituted 3-sulfonyl azaspiro[4.5]decatrienones in good yields. The developed approach has also been extended fruitfully to 3-thiocyano aza-spirocycles through domino thiocyanation/dearomative ipso-annulation.

A general and efficient approach to the synthesis of various indole-fused δ-sultones has been developed via DBU-mediated [3+3] cyclizations of indolin-3/2-ones and β-(hetero)arylethenesulfonyl fluorides. Notably, the reaction shows a broad substrate scope, and over 70 examples were exhibited in up to 99% isolated yield. In addition, some of the synthesized compounds showed significant antitumor activity against HepG2 and Caco-2 cells in vitro, which might provide promising insights for the future discovery and rational design of novel antitumor agents.