Nitrogen-containing heterocycles are essential to chemical and life sciences due to their diverse biological activities and functional versatility. However, in contrast to 3D bioisosteres of the benzene ring, analogous bioisosteres of nitrogen-containing heterocycles remain quite limited despite several recent developments, where pyridone, a “central bioisostere” for amide, phenyl, pyridine, pyridine N-oxides, and phenols, should be especially highlighted. Herein, we report an effective route for the divergent synthesis of 3-azabicyclo[3.1.1]heptan-2-ones as promising pyridone bioisosteres from bicycle-butanes (BCBs) via Ir/Lewis acid-catalyzed programmed hydrogen atom transfer of C(sp3)–H bonds and subsequent cyclization under visible light. Mechanistic evidence and DFT calculations suggest that the acid catalyst was crucial for the success via isomerizing BCBs and modulating the reactivity of the diradical intermediates to unlock a challenging carbon-to-carbon DHAT and subsequent cyclization that allows the functionalization of various C(sp3)–H bonds, accessing underexplored 3-azabicyclo[3.1.1]heptan-2-ones. Lastly, further transformations and applications in synthetic chemistry and bioactive molecules reveal their promising potential in organic synthesis, materials science, and pharmaceuticals.

Bimetallic cooperativity and synergistic effects have emerged as powerful tools that can enhance the reactivity and selectivity of catalytic systems, offering a pathway toward the development of catal...

“We give them all A’s, and they give us all fives.”

The heavier, the better! We report that the caesium congener is the most active and versatile catalyst amongst a full group set of well-defined crown ether supported alkali metal diphenyl phosphides ...

A copper-catalyzed borylative coupling of allenes with 1-trifluoromethyl alkenes is reported. The reaction selectively provides synthetically versatile borylated 1,1-difluoro-1,5-dienes that can be c....

Beilstein Journal of Organic Chemistry

Crowned! Herein we describe a complete series of crown ether coordinated alkali metal phosphides from lithium to cesium, including solid state structures, detailed investigations in solution and exte...

Sequential [2+2] cycloaddition reactions between acetylene and the digallene and diindene compounds (ETer)2 (E = Ga, In; Ter = 2,6-Dipp2-C6H3; Dipp = 2,6-diisopropylphenyl) are described. Careful con...

The intricate relationship between diradical character, aromaticity, and reactivity in annulated heavier Group 14 benzene-1,4-diides, i.e. [(ADC)E]2 (E = Si, Ge, Sn), based on an anionic dicarbene fr...

The chemical reduction of a bilayer spironanographene, spiro-NG (C137H120), with Na and K metals in the presence of [2.2.2]cryptand to yield [Na+(2.2.2-cryptand)](C137H121–) (1) and [K+(2.2.2-cryptan...

A stereoselective control of molecular nanographene helicity has been achieved by a point-to-helical chirality transfer during the Scholl graphitization reaction to obtain compound 4. Density Function...

Herein, we present a comprehensive computational study of the reaction mechanism and regioselectivity patterns of the phosphine-catalyzed Heine reaction involving N-benzoylaziridines. Density function...

The unexpected reactivity and stability limits of phosphorus ylide-based aluminum- and gallium-carbon ambiphiles are described. While the previously published t-butyl-substituted compound (2-{AltBu2}...

The impact of the nature of the Group 15 element on both the bonding situation and the reactivity of gold(I)-C ≡ E (E = N to Bi) complexes has been studied quantum chemically within the density theory...

The incorporation of saturated bioisosteres of phenyl rings has emerged as an appealing strategy in drug-discovery programmes. However, stereocontrolled access to these sp3-hybridized skeletons remain...

The reaction between NHC-supported (NHC = N-heterocyclic carbene) gold(i) trimethylsilylacetylide complexes with NHC gold(i) hydroxide species renders different symmetrical homobimetallic Au complexes...

The introduction of 4,5-dihydroazuleno[2,1,8-ija]azulene as a central core between two 1,4-dithiafulvene (DTF) units provides a novel class of extended tetrathiafulvalene (TTF) electron donors. Herei....

Although diradicals should exhibit a rather small reaction barrier as compared to closed-shell species for activating kinetically inert molecules, the activation and functionalization of carbon dioxid...

A facile photochemical, one-pot synthesis of highly functionalized 1-aminotetralins derivatives (> 70 examples) from readily accessible o-alkyl and o-formyl aryl silylimines with olefins is described...