Versatile dehydrogenation of carbonyls enabled by an iodine(III) reagent.

We report the utilisation of an iodine(III) reagent to access α,β-unsaturated carbonyls from the corresponding silyl enol ethers of ketones and aldehydes, and from enol phosphates of lactones and lactams. The transformation is rapid, scalable, and can be carried out in one pot, directly dehydrogenating saturated carbonyls.

Streamlining the Synthesis of Pyridones through Oxidative Amination of Cyclopentenones.

Herein we report the development of an oxidative amination process for the streamlined synthesis of pyridones from cyclopentenones. Cyclopentenone building blocks can undergo in situ silyl enol ether formation, followed by the introduction of a nitrogen atom into the carbon skeleton with successive aromatisation to yield pyridones. The reaction sequence is operationally simple, rapid, and carried out in one pot.

Direct Access to Quinazolines and Pyrimidines from Unprotected Indoles and Pyrroles through Nitrogen Atom Insertion.

Recent advances in single-atom insertion reactions have opened up new synthetic approaches for molecular diversification. Developing innovative strategies to directly transform biologically relevant molecules, without any prefunctionalization, is key to further expanding the scope and utility of such transformations. Herein, the direct access to quinazolines and pyrimidines from the corresponding unprotected 1-indoles and 1-pyrroles is reported, relying on the implementation of lithium bis(trimethylsilyl)amide (LiHMDS) as a novel nitrogen atom source in combination with commercially available hypervalent iodine reagents.

Nickel(I)-Phenolate Complexes: The Key to Well-Defined Ni(I) Species.

Phosphine-stabilized monovalent nickel complexes play an important role in catalysis, either as catalytically active species or as decomposition products. Most routes to access these complexes are highly ligand specific or rely on strong reducing agents. Our group recently disclosed a path to access nickel(I)-phenolate complexes from bis(1,5-cyclooctadiene)nickel(0) (Ni(cod)).

Mechanistic Investigation of the Nickel-Catalyzed Transfer Hydrocyanation of Alkynes.

The implementation of HCN-free transfer hydrocyanation reactions on laboratory scales has recently been achieved by using HCN donor reagents under nickel- and Lewis acid co-catalysis. More recently, malononitrile-based HCN donor reagents were shown to undergo the C(sp)-CN bond activation by the nickel catalyst in the absence of Lewis acids. However, there is a lack of detailed mechanistic understanding of the challenging C(sp)-CN bond cleavage step.

Skeletal metalation of lactams through a carbonyl-to-nickel-exchange logic.

Classical metalation reactions such as the metal-halogen exchange have had a transformative impact on organic synthesis owing to their broad applicability in building carbon-carbon bonds from carbon-halogen bonds. Extending the metal-halogen exchange logic to a metal-carbon exchange would enable the direct modification of carbon frameworks with new implications in retrosynthetic analysis. However, such a transformation requires the selective cleavage of highly inert chemical bonds and formation of stable intermediates amenable to further synthetic elaborations, hence its development has remained considerably challenging.

Nitrogen atom insertion into indenes to access isoquinolines.

We report a convenient protocol for a nitrogen atom insertion into indenes to afford isoquinolines. The reaction uses a combination of commercially available phenyliodine(iii) diacetate (PIDA) and ammonium carbamate as the nitrogen source to furnish a wide range of isoquinolines. Various substitution patterns and commonly used functional groups are well tolerated.

Late-stage diversification of indole skeletons through nitrogen atom insertion.

Compared with peripheral late-stage transformations mainly focusing on carbon-hydrogen functionalizations, reliable strategies to directly edit the core skeleton of pharmaceutical lead compounds still remain scarce despite the recent flurry of activity in this area. Herein, we report the skeletal editing of indoles through nitrogen atom insertion, accessing the corresponding quinazoline or quinoxaline bioisosteres by trapping of an electrophilic nitrene species generated from ammonium carbamate and hypervalent iodine. This reactivity relies on the strategic use of a silyl group as a labile protecting group that can facilitate subsequent product release.

Mechanistic Investigation of the Nickel-Catalyzed Metathesis between Aryl Thioethers and Aryl Nitriles.

Functional group metathesis is an emerging field in organic chemistry with promising synthetic applications. However, no complete mechanistic studies of these reactions have been reported to date, particularly regarding the nature of the key functional group transfer mechanism. Unraveling the mechanism of these transformations would not only allow for their further improvement but would also lead to the design of novel reactions.

Activity-Based Approach for Selective Molecular CO Sensing.

Carbon dioxide (CO) impacts every aspect of life, and numerous sensing technologies have been established to detect and monitor this ubiquitous molecule. However, its selective sensing at the molecular level remains an unmet challenge, despite the tremendous potential of such an approach for understanding this molecule's role in complex environments. In this work, we introduce a unique class of selective fluorescent carbon dioxide molecular sensors (CarboSen) that addresses these existing challenges through an activity-based approach.

One to Find Them All: A General Route to Ni(I)-Phenolate Species.

The past 20 years have seen an extensive implementation of nickel in homogeneous catalysis through the development of unique reactivity not easily achievable by using noble transition metals. Many catalytic cycles propose Ni(I) complexes as potential reactive intermediates, yet the scarcity of nickel(I) precursors and the lack of a general, non-ligand-specific protocol for their synthesis have hampered progress in this field of research. This has in turn also limited the access to novel, well-defined Ni(I) species for the development of new catalytic reactions.

An Additivity Scheme for Aromaticity: The Heteroatom Case.

The nucleus-independent chemical shift (NICS)-XY-Scan is a simple and easy tool for the quantitative measurement of the aromaticity of polycyclic aromatic hydrocarbons and identification of the existence of local and global ring currents. We recently introduced an additivity scheme that uses the NICS-XY-Scans of smaller building blocks to predict the aromatic profiles of larger polycyclic aromatic hydrocarbon systems. We now report on an expansion of the methodology to include systems of varying aromatic natures containing the heteroatoms B, N, O, and S.