Substrate-directed regioselective alkene functionalizations of ()-β,γ-unsaturated carboxylic acids.

A carboxylate-directed regioselective Heck-type alkenylation and alkenylative lactonization of ()-β,γ-unsaturated carboxylic acids by simply substrate control is reported. ()- and ()-alkenyl bromides reacted to give energetically more favorable palladacyles, allowing access to fully stereocontrolled conjugated 1,3-dienes and alkenyled γ-lactones. Mechanistic studies suggest that excellent regioselectivity may be strongly influenced by the steric factors of reactants involved in the palladacycle intermediates.

Ligand-Dominated Activation of CO and CS by the Putative Nickel Phosphiniminato Intermediates.

Room-temperature photoactivation of the first- and second-generation PNP-pincer nickel azido complexes and in the presence of CO or CS afforded N-bound carbamates, dithiocarbamates, and isothiocyanates, providing insights into CO and CS activation and demonstrating how a seemingly small difference in the ligand structure significantly influences the reactivity. Theoretical calculations disclosed that the charge of the phosphorus atom plays a critical role in determining the nitrogen atom transfer to form a plausible nickel phosphiniminato intermediate.

Selective benzylic C-H bond activations mediated by a phosphorus-nitrogen PNP-nickel complex.

In contrast to the typical C-H activation, a PNP-Nickel complex chemoselectively cleaved the benzylic C-H bond of toluene in the presence of KHMDS, presumably an generated potassium benzyl intermediate. Under similar conditions, CO underwent deoxygenation to afford the corresponding nickel cyano complex, and ethylbenzene was dehydrogenated to give styrene and a nickel hydride compound. 2,6-Xylyl isocyanide was transformed into an unprecedented indolyl complex, likely by trapping the activated benzyl species with an isocyanide moiety.

Understanding Halide Counterion Effects in Enantioselective Ruthenium-Catalyzed Carbonyl (α-Aryl)allylation: Alkynes as Latent Allenes and Trifluoroethanol-Enhanced Turnover in The Conversion of Ethanol to Higher Alcohols via Hydrogen Auto-transfer.

Crystallographic characterization of RuX(CO)(η-CH)(JOSIPHOS), where X = Cl, Br, or I, reveals a halide-dependent diastereomeric preference that defines metal-centered stereogenicity and, therefrom, the enantioselectivity of C-C coupling in ruthenium-catalyzed -diastereo- and enantioselective C-C couplings of primary alcohols with 1-aryl-1-propynes to form products of carbonyl -(α-aryl)allylation. Computational studies reveal that a non-classical hydrogen bond between iodide and the aldehyde formyl CH bond stabilizes the favored transition state for carbonyl addition. An improved catalytic system enabling previously unattainable transformations was developed that employs an iodide-containing precatalyst, RuI(CO)(η-CH), in combination with trifluoroethanol, as illustrated by the first enantioselective ruthenium-catalyzed C-C couplings of ethanol to form higher alcohols.

Aromaticity in catalysis: metal ligand cooperation via ligand dearomatization and rearomatization.

Unlike the conventional model of transition metal catalysis, ligands in metal-ligand cooperative (or bifunctional) catalysis are involved in the substrate activations. Such processes have offered unique mechanistic understandings and led to new concepts for the catalyst design. In particular, unprecedented activities were discovered when the ligand could undergo dearomatization-rearomatization reactions during the catalytic cycle.

All-Carbon Quaternary Stereocenters α to Azaarenes via Radical-Based Asymmetric Olefin Difunctionalization.

A radical-based asymmetric olefin difunctionalization strategy for rapidly forging all-carbon quaternary stereocenters α to diverse azaarenes is reported. Under cooperative photoredox and chiral Brønsted acid catalysis, cyclopropylamines with α-branched 2-vinylazaarenes can undergo a sequential two-step radical process, furnishing various valuable chiral azaarene-substituted cyclopentanes. The use of the rigid and confined -symmetric imidodiphosphoric acid catalysts achieves high enantio- and diastereo-selectivities for these asymmetric [3 + 2] cycloadditions.

Catalytic Asymmetric Formal [3+2] Cycloaddition of Azoalkenes with 3-Vinylindoles: Synthesis of 2,3-Dihydropyrroles.

Chiral phosphoric acid-catalyzed highly enantioselective formal [3 + 2] cycloaddition reaction of azoalkenes with 3-vinylindoles has been established. Under mild conditions, the projected cycloaddition proceeded smoothly, affording a variety of 2,3-dihydropyrroles in high yields and excellent enantioselectivities, and also in a diastereospecific manner. As opposed to the common 4-atom synthons in the previous literature reports, azoalkenes served as 3-atom synthons.

Asymmetric Three-Component Heck Arylation/Amination of Nonconjugated Cyclodienes.

Substituted cyclohexylamines are becoming increasingly important in drug discovery. Asymmetric Heck insertion/amination of nonconjugated cyclodienes proceeds to give 5-aryl cyclohexenylamines with good enantioselectivity and exclusive trans configurations. Primary and secondary anilines, indoline, and benzylamines are suitable amines.

Fast-Response, Highly Air-Stable, and Water-Resistant Organic Photodetectors Based on a Single-Crystal Pt Complex.

Organic semiconductors demonstrate several advantages over conventional inorganic materials for novel electronic and optoelectronic applications, including molecularly tunable properties, flexibility, low-cost, and facile device integration. However, before organic semiconductors can be used for the next-generation devices, such as ultrafast photodetectors (PDs), it is necessary to develop new materials that feature both high mobility and ambient stability. Toward this goal, a highly stable PD based on the organic single crystal [PtBr (5,5'-bis(CF CH OCH )-2,2'-bpy)] (or "Pt complex (1o)") is demonstrated as the active semiconductor channel-a material that features a lamellar molecular structure and high-quality, intraligand charge transfer.

Dearomatization of 3-Nitroindoles by a Phosphine-Catalyzed Enantioselective [3+2] Annulation Reaction.

The dearomatization of 3-nitroindoles through a chiral-phosphine-mediated [3+2] annulation reaction is described. This method makes use of readily available 3-nitroindoles as an aromatic feedstock and rapidly delivers a wide range of cyclopentaindoline alkaloid scaffolds in a highly enantioselective manner. Notably, phosphine-triggered cyclization has not been utilized previously in a dearomatization process.

Cyclometalated Iridium-PhanePhos Complexes Are Active Catalysts in Enantioselective Allene-Fluoral Reductive Coupling and Related Alcohol-Mediated Carbonyl Additions That Form Acyclic Quaternary Carbon Stereocenters.

Iridium complexes modified by the chiral phosphine ligand PhanePhos catalyze the 2-propanol-mediated reductive coupling of diverse 1,1-disubstituted allenes 1a-1u with fluoral hydrate 2a to form CF-substituted secondary alcohols 3a-3u that incorporate acyclic quaternary carbon-containing stereodiads. By exploiting concentration-dependent stereoselectivity effects related to the interconversion of kinetic ( Z)- and thermodynamic ( E)-σ-allyliridium isomers, adducts 3a-3u are formed with complete levels of branched regioselectivity and high levels of anti-diastereo- and enantioselectivity. The utility of this method for construction of CF-oxetanes and CF-azetidines is illustrated by the formation of 4a and 6a, respectively.

A Pseudodearomatized PNP*Ni-H Complex as a Ligand and σ-Nucleophilic Catalyst.

In contrast to the conventional strategy of modifying the reactivities and selectivities of the transition metal and organocatalysts by varying the steric and electronic properties of organic substituent groups, we hereby demonstrate a novel approach that the sigma (σ) nucleophilicity of the imine arm can be significantly enhanced in a pseudodearomatized PNP* pincer ligand platform to reach unprecedented N-heterocyclic carbene-like reactivity. Accordingly, the imine arm of the PNP*Ni-H pincer complex efficiently catalyzes the hydrosilylation of aldehydes, cycloaddition of carbon dioxide (CO) to epoxides, and serves as a ligand in the Ru-catalyzed dehydrogenative acylation of amines with alcohols.

Glaulactams A-C, daphniphyllum alkaloids from Daphniphyllum glaucescens.

Glaulactams A-C (1-3), which possess a novel skeleton, as well as the known compound daphmanidin B (4), were isolated from the leaves of Daphniphyllum glaucescens and separated using ion-exchange chromatography aided by NMR fingerprinting. Their structures, including their absolute configurations, were elucidated by spectroscopic analyses and time-dependent density-functional-theory-calculated electronic circular dichroism spectra; the data were subsequently analyzed to gain insight into the respective biogenetic relationships between the isolates, which exhibited anti-H1N1 and immunosuppressive activities.

Diverse catalytic reactivity of a dearomatized PNP*-nickel hydride pincer complex towards CO reduction.

A dearomatized PN3P*-nickel hydride complex has been prepared using an oxidative addition process. The first nickel-catalyzed hydrosilylation of CO2 to methanol has been achieved, with unprecedented turnover numbers. Selective methylation and formylation of amines with CO2 were demonstrated by such a PN3P*-nickel hydride complex, highlighting its versatile functions in CO2 reduction.

Metal-Ligand Cooperative Reactivity in the (Pseudo)-Dearomatized PN(P) Systems: The Influence of the Zwitterionic Form in Dearomatized Pincer Complexes.

The concept of aromaticity in pincer ligands and complexes was discussed in order to provide insights into their metal-ligand cooperative activities. The aromatic PN(P) and dearomatized PN(P)* pincer ligands and the corresponding transition metal complexes were studied with the nucleus-independent chemical shift (NICS), anisotropy of the current (induced) density (ACID), isochemical shielding surfaces (ICSS), harmonic oscillator model of aromaticity (HOMA), MCBO, Shannon aromaticity, and natural bond order (NBO) analyses. The study on the model systems showed that for the dearomatized species the decrease of the NICS(1) value comes with the larger contribution of the aromatic zwitterionic mesomeric form.

Benzo[4,5]cyclohepta[1,2-]fluorene: an isomeric motif for pentacene containing linearly fused five-, six- and seven-membered rings.

Benzo[4,5]cyclohepta[1,2-]fluorene (), a new π-conjugated polycyclic hydrocarbon containing linearly fused six-, five-, six-, seven- and six-membered rings (C-C-C-C-C), was designed and its stable derivatives and were synthesized. With 22 π electrons, is an isomer of pentacene with quinoidal, dipolar ionic and diradical resonance forms. Molecules and were experimentally investigated with cyclic voltammetry, electronic absorption spectroscopy and X-ray crystallographic analysis, and theoretically studied by calculating the NICS value, diradical character and dipole moment.

Super-heptazethrene.

The challenging synthesis of a laterally extended heptazethrene molecule, the super-heptazethrene derivative SHZ-CF3, is reported. This molecule was prepared using a strategy involving a multiple selective intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation. Compound SHZ-CF3 exhibits an open-shell singlet diradical ground state with a much larger diradical character compared with the heptazethrene derivatives.

Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure.

The fundamental relationship between structure and diradical character is important for the development of open-shell diradicaloid-based materials. In this work, we synthesized two structural isomers bearing a 2,6-naphthoquinodimethane or a 1,5-naphthoquinodimethane bridge and demonstrated that their diradical characters and chemical reactivity are quite different. The mesityl-or pentafluorophenyl-substituted octazethrene derivatives OZ-M/OZ-F and their isomer OZI-M (with mesityl substituents) were synthesized via an intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation strategy from the key building blocks 4 and 11.

Toward Tetraradicaloid: The Effect of Fusion Mode on Radical Character and Chemical Reactivity.

Open-shell singlet diradicaloids display unique electronic, nonlinear optical, and magnetic activity and could become novel molecular materials for organic electronics, photonics, and spintronics. However, design and synthesis of diradicaloids with a significant polyradical character is a challenging task for chemists. In this Article, we report our efforts toward a tetraradicaloid system.

Exploring diradical chemistry: a carbon-centered radical may act as either an anion or electrophile through an orbital isomer.

Diradical intermediates, formed by thermolysis of alkynylcyclobutenones, can display radical, anion, or electrophilic character because of the existence of an orbital isomer with zwitterionic and cyclohexatrienone character. Our realization that water, alcohols, and certain substituents can induce the switch provides new opportunities in synthesis. For example, it can be used to shut down radical pathways and to give access to aryl carbonates and tetrasubstituted quinones.

Organoytterbium ate complexes extend the value of cyclobutenediones as isoprene equivalents.

Changing course: While organolithium and Grignard reagents favor addition to C1 of A (R=Me), the corresponding organoytterbium reagents add to C2 (R=tBu). Computational studies provide insights into the nature of organoytterbium species and their reactivity, and a total synthesis of (-)-mansonone B illustrates the utility of the method in terpenoid synthesis. Tf=trifluoromethanesulfonyl.

New insights into cyclobutenone rearrangements: a total synthesis of the natural ROS-generating anti-cancer agent cribrostatin 6.

Aryl- and heteroarylcyclobutenone rearrangements proceed in excellent yield under continuous-flow conditions. The former shows a Hammett correlation with σ(I) providing strong evidence that electrocyclisation is the rate-determining step and has a late transition state. The reaction has been modelled by using DFT and CCSD(T) methods, with the latter giving excellent correlation with the experimental rate constant.