Nickel-Catalyzed C-N Cross-Coupling of 4-Chloro-1,8-naphthalimides and Bulky, Primary Alkylamines at Room Temperature.

4-Amino-1,8-naphthalimides, potentially useful fluorescent probes in biological applications, are prepared via Ni(cod)2/IPr-catalyzed cross-couplings between 4-chloro-1,8-naphthalimide electrophiles and α,α,α-trisubstituted, primary alkylamines at room temperature. This method represents the first synthesis of 4-amino-1,8-naphthalimides using Ni-catalyzed C-N cross-coupling and provides the first examples of 4-amino-1,8-naphthalimides incorporating such bulky primary alkylamines, thereby highlighting the utility of Ni-catalyzed processes in synthesizing naphthalimide scaffolds that were inaccessible using established methods (SNAr; Pd or Cu catalysis).

Mapping Dual-Base-Enabled Nickel-Catalyzed Aryl Amidations: Application in the Synthesis of 4-Quinolones.

The C-N cross-coupling of (hetero)aryl (pseudo)halides with NH substrates employing nickel catalysts and organic amine bases represents an emergent strategy for the sustainable synthesis of (hetero)anilines. However, unlike protocols that rely on photoredox/electrochemical/reductant methods within NiI/III cycles, the reaction steps that comprise a putative Ni0/II C-N cross-coupling cycle for a thermally promoted catalyst system using organic amine base have not been elucidated. Here we disclose an efficient new nickel-catalyzed protocol for the C-N cross-coupling of amides and 2'-(pseudo)halide-substituted acetophenones, for the first time where the (pseudo)halide is chloride or sulfonate, which makes use of the commercial bisphosphine ligand PAd2-DalPhos (L4) in combination with an organic amine base/halide scavenger, leading to 4-quinolones. Room-temperature stoichiometric experiments involving isolated Ni0, I, and II species support a Ni0/II pathway, where the combined action of DBU/NaTFA allows for room-temperature amide cross-couplings.

Air and water stable secondary phosphine oxides as diazaphospholene precatalysts.

Air-stable secondary phosphine oxides (SPOs) are readily formed from diazaphospholene bromides. In the presence of pinacolborane, these SPOs are transformed into catalytically active diazaphospholene hydrides. A silyl triflate transforms the SPOs into phosphenium triflates. The use of diazaphospholene SPOs as reduction reaction precatalysts was validated by imine reduction, conjugate reduction, pyridine hydroboration, and asymmetric reduction.

Enantioselective Imine Reduction Catalyzed by Phosphenium Ions.

The first use of phosphenium cations in asymmetric catalysis is reported. A diazaphosphenium triflate, prepared in two or three steps on a multigram scale from commercially available materials, catalyzes the hydroboration or hydrosilylation of cyclic imines with enantiomeric ratios of up to 97:3. Catalyst loadings are as low as 0.2 mol %. Twenty-two aryl/heteroaryl pyrrolidines and piperidines were prepared using this method. Imines containing functional groups such as thiophenes or pyridyl rings that can challenge transition-metal catalysts were reduced employing these systems.

Activation and deprotection of F-BODIPYs using boron trihalides.

The activation of F-BODIPYs with boron trihalides, followed by treatment with a nucleophile, effects facile substitution at boron; using water as the nucleophile promotes deprotective removal of the -BF2 moiety and thereby production of the corresponding parent dipyrrin salt in quantitative yield under extremely mild conditions.

Chiral induction at octahedral Ru(II) via the disassembly of diruthenium(II,III) tetracarboxylates using a variety of chiral diphosphine ligands.

Achiral [Ru2(µ-O2CR)4(MeOH)2](PF6) (R = CH3 or C6H5) reacts with the chiral diphosphines R,R- and S,S-Chiraphos (two chiral centers on ligand between the coordinating P atoms) and R-Prophos (one chiral center on ligand between the coordinating P atoms) leading to a disassembly of the paddlewheel core and the highly diastereoselective production of Λ-[Ru(η(2)-O2CC6H5)(η(2)-R,R-Chiraphos)2](PF6) (Λ-R,R-III), Δ-[Ru(η(2)-O2CC6H5)(η(2)-S,S-Chiraphos)2](PF6) (Δ-S,S-III) (the R = CH3 complexes of Chiraphos were reported in a earlier communication in this journal), and Λ-[Ru(η(2)-O2CCH3)(η(2)-R-Prophos)2](PF6) (Λ-R,R-VI), respectively, in high yield and purity. Reactions of the same starting material with R,R- and S,S-o-tolyl-Dipamp (chiral centers are the coordinating P-atoms) lead to an inversion in the chirality-at-metal producing Λ-[Ru(η(2)-O2CC6H5)(η(2)-S,S-o-tolyl-Dipamp)2](PF6) (Λ-S,S-IV), Δ-[Ru(η(2)-O2CC6H5)(η(2)-R,R-o-tolyl-Dipamp)2](PF6) (Δ-R,R-IV), Λ-[Ru(η(2)-O2CCH3)(η(2)-S,S-o-tolyl-Dipamp)2](PF6) (Λ-S,S-V), and Δ-[Ru(η(2)-O2CCH3)(η(2)-R,R-o-tolyl-Dipamp)2](PF6) (Δ-R,R-V). X-ray crystallography of all but Λ-S,S-V and Δ-R,R-V and solid-state circular dichroism (CD) show that only the indicated diastereomers are present in the solid-state. Solution CD measurements and (31)P NMR also indicate their predominance in solution.

Synthesis and characterisation of the unsubstituted dipyrrin and 4,4-dichloro-4-bora-3a,4a-diaza-s-indacene: improved synthesis and functionalisation of the simplest BODIPY framework.

An improved and scalable synthesis of the unsubstituted 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene framework facilitates access to the previously unreported parent dipyrrin HCl salt, as well as 4,4-dichloro-4-bora-3a,4a-diaza-s-indacene.

Conversion of F-BODIPYs to Cl-BODIPYs: enhancing the reactivity of F-BODIPYs.

A new method for the synthesis of Cl-BODIPYs from F-BODIPYs is reported, merely requiring treatment of the F-BODIPY with boron trichloride. Cl-BODIPYs are exploited as synthetic intermediates generated in situ for the overall conversion of F-BODIPYs to O- and C-BODIPYs in high overall yields using a mild one-pot procedure. This route enables F-BODIPYs to be transformed into derivatives that are not accessible via the direct route, as demonstrated via the use of 1,3-propanediol.

An improved method for the synthesis of F-BODIPYs from dipyrrins and bis(dipyrrin)s.

An improved methodology for the synthesis of F-BODIPYs from dipyrrins and bis(dipyrrin)s is reported. This strategy employs lithium salts of dipyrrins as intermediates that are then treated with only 1 equiv of boron trifluoride diethyletherate to obtain the corresponding F-BODIPYs. This scalable route to F-BODIPYs renders high yields with a facile purification process involving merely filtration of the reaction mixture through Celite in many cases.

Cl-BODIPYs: a BODIPY class enabling facile B-substitution.

Cl-BODIPYs, synthesized in high yields from dipyrrins under air- and moisture-free conditions, are extremely facile to substitution at boron compared to their corresponding F-BODIPYs, opening up a new route to BODIPYs functionalized at boron.