https://advanced.onlinelibrary.wiley.com/doi/10.1002/advs.76530

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Visible-Light-Mediated Lewis Acid-Catalyzed Diradical Hydrogen Atom Transfer Reaction of Bicyclo[1.1.0]butanes

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.

pubs.acs.org

pubs.rsc.org

Snapshots of Cooperative Trimetallic Alkene Hydrogenation

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...

pubs.acs.org

How Teacher Evaluations Broke the University

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

theatlantic.com

Heavyweight Champion: Caesium Diorganophosphides Outperform Lighter Congeners in the Catalytic Hydrophosphination of Alkenes and Alkynes

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 ...

onlinelibrary.wiley.com

Copper‐Catalyzed Defluorinative Allylboration of Allenes with Trifluoromethyl Alkenes

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....

chemistry-europe.onlinelibrary.wiley.com

Transition-state aromaticity and its relationship with reactivity in pericyclic reactions

Beilstein Journal of Organic Chemistry

beilstein-journals.org

Crown Ether Supported Alkali Metal Phosphides: Synthesis, Structures and Bonding

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...

chemistry-europe.onlinelibrary.wiley.com

Stepwise Acetylene Insertion and Ammonia Activation at a Digallene and Diindene

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...

onlinelibrary.wiley.com

Understanding Small Molecule Activation Promoted by Heavier Benzene 1,4‐diides: Interplay between Diradical Character and Aromaticity

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...

chemistry-europe.onlinelibrary.wiley.com

Reduction‐Induced C–C Cleavage and Site‐Specific Hydrogenation of a Highly Strained Bilayer Spironanographene.

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...

doi.org

Diastereoselective Scholl reaction: Point-to-helical chirality transfer in molecular nanographenes

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...

pubs.rsc.org

Mechanism and Origin of Regioselectivity in the Phosphine-Catalyzed Heine Reaction

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...

pubs.acs.org

Stabilities and Limitations in the Reactivity of Phosphorus Ylide‐Based Aluminum‐ and Gallium‐Carbon Ambiphiles − A Combined Experimental and Computational Approach

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}...

doi.org

Influence of the Nature of Group 15 Element on [AuI]–C≡E/Azide 1,3-Dipolar Cycloaddition Reaction

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...

pubs.acs.org

Enantioselective photocatalytic synthesis of bicyclo[2.1.1]hexanes as ortho-disubstituted benzene bioisosteres with improved biological activity - Nature Chemistry

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...

nature.com

Stepwise alkyne insertion in Au(I) acetylides: influence of the nuclearity

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...

pubs.rsc.org

Extended Tetrathiafulvalene Multi‐Redox Systems Incorporating 4,5‐Dihydroazuleno[2,1,8‐ija]azulene Cores

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....

onlinelibrary.wiley.com

Structural Snapshots of Reversible Carbon Dioxide Capture and (De)oxygenation at Group 14 Diradicaloids

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...

pubs.acs.org