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2-Aminobiphenyl palladacycles are among the most successful precatalysts for Pd-catalyzed cross-coupling reactions, including aryl amination. However, the role of NH-carbazole, a byproduct of precatalyst activation, remains poorly understood. Herein, the mechanism of the aryl amination reactions catalyzed by a cationic 2-aminobiphenyl palladacycle supported by a terphenyl phosphine ligand, PCyp2ArXyl2 (Cyp = cyclopentyl; ArXyl2 = 2,6-bis(2,6-dimethylphenyl)phenyl), P1, has been thoroughly investigated. Combining computational and experimental studies, we found that the Pd(II) oxidative addition intermediate reacts with NH-carbazole in the presence of the base (NaOtBu) to yield a stable aryl carbazolyl Pd(II) complex. This species functions as the catalyst resting state, providing the amount of monoligated LPd(0) species required for catalysis and minimizing Pd decomposition. In the case of a reaction with aniline, an equilibrium between the carbazolyl complex and the on-cycle anilido analogue is established, which allows for a fast reaction at room temperature. In contrast, heating is required in a reaction with alkylamines, whose deprotonation involves coordination to the Pd center. A microkinetic model was built combining computational and experimental data to validate the mechanistic proposals. In conclusion, our study shows that despite the rate reduction observed in some reactions by the formation of the aryl carbazolyl Pd(II) complex, this species reduces catalyst decomposition and could be considered an alternative precatalyst in cross-coupling reactions., The authors thank MCIN/AEI/ 10.13039/501100011033 (Grant PID2020-113797R), US/JUNTA/FEDER, UE (Grant US-1262266), and FEDER/Junta de Andalucía-Consejería de Economía y Conocimiento (Grant P20_00624) for the financial support. R.J.R. and A.N. acknowledge the support from the Research Council of Norway through the Centre of Excellence (No. 262695) and A.N. for its FRINATEK program (314321). R.J.R. thanks the Universidad de Sevilla (V and VI Plan Propio de Investigación) for research fellowships. R.J.R. thanks the Norwegian Metacenter for Computational Science (NOTUR) for computational resources (No. nn4654k). Thanks are also due to Nazaret Santamaría for helping with kinetic experiments.

Herein we describe a phosphine-catalyzed internal redox [4 + 2] annulation of 1,4-enynoates with electron-deficient alkenes, in which the γ- and φ-C(sp3)-H of the enynoates are formally oxidized for the annulation while the alkynyl moiety is converted to an alkene. The reaction offers an efficient synthesis of highly functionalized cyclohexenes in moderate to good yields with exclusive regioselectivity and high diastereoselectivity under mild conditions.

The fac-[M(CO)3(PyA)(P)] and cis-trans-[M(CO)2(PyA)(P)2] neutral complexes (M is Re or 99mTc), based on the mixed ligand strategy with pyrazine-2-carboxylic acid (PyAH) as the bidentate N,O and triphenylphosphine as the monodentate P ligand, are presented. Through the employment of the anhydride of pyrazine-2,3-dicarboxylic acid (PyDA), the PyAH scaffold was conveniently derivatized with the model bioactive amine 1-(2-methoxyphenyl)piperazine, the active part of the 5-HT1A antagonist WAY100635. Reaction of either PyAH or the pharmacophore-bearing PyAH ligand (L1H) with fac-[M(CO)3]+ core in water yielded the intermediate fac-[M(CO)3(PyA)(H2O)] complexes. The labile aqua ligand was easily replaced by PPh3 to yield the fac-[Re(CO)3(PyA)(PPh3)] complexes, while in toluene under reflux, the cis-trans-[Re(CO)2(PyA)(PPh3)2] complexes were obtained. The latter complexes were alternatively obtained from mer-[Re(CO)3(PPh3)2Cl] by refluxing with the PyA ligand in toluene. The analogous 99mTc complexes were synthesized quantitatively, showing excellent stability in competition studies. The methodology described herein represents a practical procedure for the effective integration of the fac-[M(CO)3]+ core with amine-bearing biologically active compounds for diagnosis/therapy.

Under catalysis by chiral phosphine, an asymmetric isomerization/annulation cascade reaction of allylamines with allenoates was realized. A wide range of γ-substituted allenoates were tolerated to afford chiral pyrroline derivatives in high yields with excellent enantioselectivities. In the reaction, isomerization of readily available N-allylamines to reactive aliphatic imines through a 1,4-proton shift is a key step, which circumvents the isolation of highly unstable alkyl N-sulfonylimines.

Anionic N-heterocyclic olefins (aNHOs) are suited well for the stabilization of low-coordinate inorganic complexes, due to their steric tunability and strong σ- and π-electron donating abilities. In this study, the new two-coordinate zinc complex (MeIPrCH)2Zn (MeIPrCH = [(MeCNDipp)2C═CH]-, Dipp = 2,6-diisopropylphenyl) is shown to participate in a broad range of metathesis reactions with main group element-based halides and hydrides. In the case of the group 14 halides, Cl2E·dioxane (E = Ge and Sn), transmetalation occurs to form dinuclear propellane-shaped cations, [(MeIPrCHE)2(μ-Cl)]+, while the aNHO-capped phosphine ligand MeIPrCH-PPh2 is obtained when (MeIPrCH)2Zn is combined with ClPPh2. Lastly, ZnH2 elimination drives transmetalation between (MeIPrCH)2Zn and hydroboranes and hydroalumanes, leading to Lewis acidic aNHO-supported -boryl and -alane products.

We describe a general and efficient protocol for the synthesis of organophosphine compounds from phenols and phosphines (R2PH) via a metal-free C-O bond cleavage and C-P bond formation process. This approach exhibits broad substrate scope and excellent functional group tolerance. The synthetic utilities of this protocol were demonstrated by the synthesis of chiral ligands via the various transformations of cyano groups and their applications in asymmetric catalysis.

The asymmetric synthesis of P-stereogenic phosphinates through allylic alkylation of H-phosphinates has been developed. With H-phosphinates and allylic acetates as the starting materials, a variety of allylic P-chiral phosphinates were accessed in high enantioselectivities of up to 92% ee and generally high yields. In addition, a further study demonstrated the applicability of this protocol, including the scale-up synthesis and facile transformation of chiral products from phosphinates to phosphine oxides with organolithium reagents under mild reaction conditions.

Various cis-s-phosphinolactams are synthesized stereoselectively for the first time from imines and diazo(aryl)methyl(diaryl)phosphine oxides under microwave irradiation. Diazo(aryl)methyl(diaryl)phosphine oxides first undergo the Wolf rearrangement to generate phosphenes. Imines nucleophilically attack the phosphenes followed by an intramolecular nucleophilic addition via less steric transition states to give final cis-s-phosphinolactams. C-Styrylimines generally give rise to s-phosphinolactams in higher yields than C-arylimines. The stereoselectivity and proposed mechanism are rationalized by DFT theoretical calculation.

The replacement of phosphine substituents in nickel-bound PNNP ligands is reported as an alternative method for preparing multidentate phosphine ligands with alkyl substituents. Treatment of the previously reported bis(phosphide) complex {K(THF)x}22Ph[PNNP]Ni (2) with 2 equiv of MeI, iPrI, and 1,3-dibromoethane formed alkyl-substituted complexes 2Ph,2Me[PNNP]Ni (3), 2Ph,2iPr[PNNP]Ni (4), and 2Ph,propylene[PNNP]Ni (5), respectively. The stereoselectivity (racemic vs meso) of these reactions can be controlled by varying the reaction temperature. The racemic mixtures of products with the new alkyl substituents in an anti configuration were favored at lower temperatures, whereas a larger proportion of meso compounds was acquired at higher temperatures. Further treatment of 3 with KH resulted in selective elimination of the remaining phenyl groups rather than the methyl substituents, affording bis(methylphosphide) complex {K(THF)x}22Me[PNNP]Ni (6). Subsequent treatment of 6 with additional MeI formed 4Me[PNNP]Ni (7), in which all four phenyl groups were replaced with methyl substituents. As a proof of concept, demetalation of the ligand from 7 was achieved using aqueous KCN to form a free dimethylphosphine-substituted ligand H24Me[PNNP] (8), and 8 was subsequently coordinated to a different metal, using PdCl2 to form 4Me[PNNP]Pd (9). Unlike the clean elimination of phenyl substituents from 3, the reactions of KH with 4 and 5 exhibited competitive elimination of both alkyl and phenyl substituents and/or attenuated reactivity.

New strategies to access radicals from common feedstock chemicals hold the potential to broadly impact synthetic chemistry. We report a dual phosphine and photoredox catalytic system that enables direct formation of sulfonamidyl radicals from primary sulfonamides. Mechanistic investigations support that the N-centered radical is generated via α-scission of the P-N bond of a phosphoranyl radical intermediate, formed by sulfonamide nucleophilic addition to a phosphine radical cation. As compared to the recently well-explored β-scission chemistry of phosphoranyl radicals, this strategy is applicable to activation of N-based nucleophiles and is catalytic in phosphine. We highlight application of this activation strategy to an intermolecular anti-Markovnikov hydroamination of unactivated olefins with primary sulfonamides. A range of structurally diverse secondary sulfonamides can be prepared in good to excellent yields under mild conditions.

Tripalladium clusters of the type [Pd3(PPh3)4]2+, wherein three linearly connected Pd atoms are stabilized by phosphine and arsine ligands, have been detected and isolated as intermediates during the reduction of well-defined mononuclear [Pd(OTf)2(XPh3)2] (X = P and X = As, respectively) to Pd nanoparticles (PdNPs). The isolated [Pd3(PPh3)4]2+ cluster isomerizes on broad-band UV irradiation to form an unexpected photoisomer, produced by a remarkable change in conformation at one of the bridging PPh3 ligands. A catalytic role for these [Pd3(XPh3)4]2+ species is exemplified in Suzuki-Miyaura cross-coupling (SMCC) reactions, with high activity seen in the arylation of a brominated heterocyclic 2-pyrone. Use of the [Pd3(PPh3)4]2+ cluster enables a switch in site selectivity for SMCC reactions involving 2,4-dibromopyridine from the typical C2-bromide site (seen previously for mononuclear Pd catalysts) to the atypical C4-bromide site, thereby mirroring recently reported cyclic Pd3 clusters and PdNPs. We have further determined that the thermal isomer and photoisomer of [Pd3(PPh3)4]2+ are similarly catalytically active in the Pd-catalyzed hydrogenation of phenylacetylene to give styrene. Our findings link the evolution of mononuclear Pd(II) salts to PdNPs via the intermediacy of linear [Pd3(XPh3)4]2+ clusters.

With the aim of developing novel annulations via ketene intermediates, allenyl imide and alkynoates bearing good leaving groups are used for their function in a tandem conjugate addition-elimination reaction (SN2' type) promoted by nucleophilic phosphine catalysts. By utilizing thioamides as 1S,3N-bis-nucleophiles, [3+3] and [3+2] annulations have been established to allow rapid access to 1,3-thiazin-4-ones and 5-alkenyl thiazolones in high yields, respectively. Furthermore, the possible reaction mechanisms are proposed on the basis of deuterium labeling experiments and density functional theory calculations.

The hydrogen/halogen exchange of phosphines has been exploited to establish a truly useable substrate scope and straightforward methodology for the formation of cyclopolyphosphines. Starting from a single dichlorophosphine, a sacrificial proton “donor phosphine” makes the rapid, mild synthesis of cyclopolyphosphines possible: reactions are complete within 10 min at room temperature. Novel (aryl)cyclopentaphosphines (ArP)5 have been formed in good conversion, with the crystal structures presented. The use of catalytic quantities of iron(III) acetylacetonate provides significant improvements in conversion in the context of diphosphine (Ar2P)2 and alkyl-substituted cyclotetra- or cyclopentaphosphine ((AlkylP)n, where n = 4 or 5) formation. Both iron-free and iron-mediated reactions show high levels of selectivity for one specific ring size. Finally, investigations into the reactivity of Fe(acac)3 suggest that the iron species is acting as a sink for the hydrochloric acid byproduct of the reaction.

Secondary phosphine oxides incorporating various aryl and alkyl groups were synthesized in racemic form, and these products formed the library reported in this study. TADDOL derivatives were used to obtain the optical resolution of these P-stereogenic secondary phosphine oxides. The developed resolution method showed a good scope under the optimized reaction conditions, as 9 out of 14 derivatives could be prepared with an enantiomeric excess (ee) ≥ 79% and 5 of these derivatives were practically enantiopure >P(O)H compounds (ee ≥ 98%). The scalability of this resolution method was also demonstrated. Noncovalent interactions responsible for the formation of diasteromeric complexes were elucidated by single-crystal XRD measurements. (S)-(2-Methylphenyl)phenylphosphine oxide was transformed to a variety of P-stereogenic tertiary phosphine oxides and a thiophosphinate in stereospecific Michaelis-Becker, Hirao, or Pudovik reactions.

We explored the traceless Staudinger ligation for the functionalization of the C2 position of second generation β-lactamase inhibitors based on a diazabicyclooctane (DBO) scaffold. Our strategy is based on the synthesis of phosphine phenol esters and their ligation to an azido-containing precursor. Biological evaluation showed that this route provided access to a DBO that proved to be superior to commercial relebactam for inhibition of two of the five β-lactamases that were tested.

A family of axially chiral azepine-containing seven-membered cyclic P,N-ligands (named Indole-azepinap) have been prepared by using l-alanine as an original chirality source. The direct chromatographic separation of two diastereomeric phosphine oxides on silica gel enabled these ligands to be easy available, allowing further structural and electronic modifications. Preliminary application of these Indole-azepinaps has been demonstrated in a Pd-catalyzed asymmetric allylic alkylation with high yields and moderate enantioselectivities.

A phosphine-catalyzed oligomerization of arynes using selenocyanates was developed. The use of JohnPhos as a bulky phosphine is the key to accessing α,ω-bisfunctionalized oligo(ortho-arylenes) with RSe as the substituent at one terminus and CN as the substituent at the other. The in situ formation of R3PSeR' cations, serving as sterically encumbered electrophiles, hinders the immediate reaction that affords the 1,2-bisfunctionalization product and instead opens a competitive pathway leading to oligomerization. Various optimized conditions for the predominant formation of dimers, but also for higher oligomers such as trimers and tetramers, were developed. Depending on the electronic properties of the electrophilic reaction partner, even compounds up to octamers were isolated. Optimization experiments revealed that a properly tuned phosphine as catalyst is of crucial importance. Mechanistic studies demonstrated that the cascade starts with the attack of cyanide; aryne insertion into n-mers leading to (n+1)-mers was ruled out.

Herein, efficient chiral recognition of phosphine oxides with octahedral indium complexes was demonstrated. Direct chiral analysis of in situ-prepared phosphine oxides formed using phosphines and hydrogen peroxide was conducted effectively via 31P nuclear magnetic resonance spectroscopy. Sufficient peak resolution of chiral phosphines was obtained consistently, thereby enabling the reliable determination of absolute chirality. Rational 1:1 binding models based on experiments and density functional theory calculations have been proposed.

We present a strategy for the synthesis of spirocyclic cyclobutanes with modulable exit vectors based on the regioselective monoborylation of spirocyclobutenes. Using an inexpensive copper salt and a commercially available bidentate phosphine, a broad variety of borylated spirocycles have been prepared with complete regiocontrol. The boryl moiety provides a synthetic handled for further functionalization, allowing access to a wide array of spirocyclic building blocks from a common intermediate, We thank the European Research Council (ERC-337776) and MINECO and MICIIN (CTQ2016-78779-R and PID2019-107380GB-I00 to M.T.; PID2019106184GB-I00 and RED2018-102387-T to I.F.) for financial support. L.N. thanks Comunidad de Madrid for a predoctoral fellowship. We acknowledge Dr. Josefina Perles (UAM) for X-ray structure análisis

We report a strategy for the orthogonal conjugation of the vinyl nucleosides, 5-vinyluridine (5-VU) and 2-vinyladenosine (2-VA), via selective reactivity with maleimide and tris(2-carboxyethyl)phosphine (TCEP), respectively. The orthogonality was investigated using density functional theory (DFT) and confirmed by reactions with vinyl nucleosides. Further, these chemistries were used to modify RNA for fluorescent cell imaging. These reactions allow for the expanded use of RNA metabolic labeling to study nascent RNA expression within different RNA populations.

A general practical approach to hetero(aromatic) and aliphatic P(O)Me2-substituted derivatives is elaborated. The key synthetic step was a [Pd]-mediated C-P coupling of (hetero)aryl bromides/iodides with HP(O)Me2. The P(O)Me2 substituent was shown to dramatically increase solubility and decrease lipophilicity of organic compounds. This tactic was used to improve the solubility of the antihypertensive drug prazosin without affecting its biological profile.

We introduce a new reagent class, 2-azatrienes, as a platform for catalytic enantioselective synthesis of allylic amines. Herein, we demonstrate their promise by a diastereodivergent synthesis of syn- and anti-1,2-diamines through their Cu-bis(phosphine)-catalyzed reductive couplings with imines. With Ph-BPE as the supporting ligand, anti-diamines are obtained (up to 91% yield, >20:1 dr, and >99:1 er), and with the rarely utilized t-Bu-BDPP, syn-diamines are generated (up to 76% yield, 1:>20 dr, and 97:3 er).

A laboratory project to introduce upper-level undergraduates to Pd-catalyzed C–N σ-bond forming reactions is described. The exercise involves evaluation of monodentate phosphine ligands and solvents for the Buchwald–Hartwig coupling of 4-chloro- or 4-bromo-anisole with morpholine. Students gain experience in the synthesis of a biarylphosphine ligand, performing reactions under anhydrous and anaerobic conditions, with systematic screening and analysis of reaction conditions, and with the use of GC–MS data to gauge the extent of each coupling reaction. Students develop arguments from spectroscopic evidence to support claims regarding the effectiveness of each set of reaction conditions and explore the impact of the ligand within the context of currently accepted mechanistic models. Optimal conditions are determined and used for the scaled-up synthesis of the coupling product, and electronic aspects of the product are explored via computational chemistry.

Identifying intermediates of Ni-containing reactions can be challenging due to the high reactivity of Ni complexes and their sensitivity toward air and moisture. Many Ni bidentate phosphine complexes are diamagnetic and can be analyzed in situ via 31P NMR spectroscopy, but the oxidation state of Ni is difficult to determine using 31P chemical shift analysis alone. The J-coupling between P atoms, JPP, has been proposed to correlate with oxidation state, but few investigations have looked at how JPP is affected by parameters such as length of the linker or identity of the phosphine or other ligands. The present investigation into the JPP values of Ni bidentate phosphine complexes with two-carbon and three-carbon linkers shows that the JPP values observed in 31P NMR spectra, |JPP|, are competent indicators of the oxidation state at Ni. For complexes with two-carbon linkers, |JPP| > 40 Hz is typical of Ni0 while |JPP| < 30 Hz is typical of NiII; this trend is reversed for complexes with three-carbon linkers. Additionally, the Lewis acidity of the Ni and Lewis basicity of the phosphine ligand affect JPP predictably. For example, increased P-to-Ni donation arising from more-donating phosphines or more-withdrawing ligands trans to the P atoms causes a more negative JPP. These results should enable the oxidation state of Ni and properties of ligands in Ni bidentate phosphine complexes to be determined in situ during reactions containing these species.

The energy conversion efficiency (η) of silicon heterojunction (SHJ) solar cells is limited by the current losses in the layer stack on the illuminated side. To reduce these losses, hydrogenated nanocrystalline silicon oxide (nc-SiOx:H) was implemented as a window layer in SHJ solar cells. However, the integration of nc-SiOx:H in devices without degradation of fill factor (FF) is still a challenge. To optimize the electron performance of devices, the optoelectronic properties and microstructure of nc-SiOx:H were characterized and analyzed systematically. It was found that the PH3 gas fraction (fPH3) plays a big role on the microstructure, oxygen content, and phosphorus (P) doping efficiency of the films. The highest conductivity, 2.84 × 10–1 S/cm, is obtained at a moderate fPH3 with an optical band gap of 2.26 eV. A ternary model was creatively used to show the variation in the composition of nc-SiOx:H as tuning fPH3. The growth of crystalline phase was accelerated by the P dopants when fPH3 is low, but further increasing fPH3 leads to excessive P inactive dopants, causing a phase transition from nanocrystalline silicon to amorphous silicon in nc-SiOx:H. In this work, the best solar cell with an nc-SiOx:H window layer achieves an FF of 81.4%, a short current density (Jsc) of 39.8 mA/cm2, an open-circuit voltage (Voc) of 731 mV, and an η of 23.7% at the moderate fPH3. A decrease in FF and Jsc is shown with higher fPH3, which is the consequence of the increased front contact resistivity and decreased optical band gap of nc-SiOx:H window layer.

Chiral chromophores and their ordered assemblies are intriguing for yielding circularly polarized luminescence (CPL) and exploring intrinsic structure-light emission relationships. With the extensively studied chiral organic molecules and inorganic nanoparticle assemblies for the amplified CPL, the assemblies of copper halide hybrid clusters have attracted intensive attention due to their potential efficient CPL. Here, we report robust chiral phosphine-copper iodide hybrid clusters and their layered assemblies in crystalline states for amplified CPL. We reveal that the intermolecular interactions endow the clusters with the capability of assembling into chiral crystalline CPL materials, including hexagonal platelet-shaped microcrystals (glum ≈ 9.5 × 10-3) and highly oriented crystalline films (glum ≈ 5 × 10-3). Owing to the high crystalline feature of the thin film, we demonstrate an electroluminescent device with bright electroluminescence (1200 cd m-2).

α,β-Butenolides with ≥96% enantiomeric excess are synthesized from β,γ-butenolides via a novel Cu(I)-ligand cooperative catalysis. The reaction is enabled by a chiral biphenyl-2-ylphosphine ligand featuring a remote tertiary amino group. Density functional theory studies support the cooperation between the metal center and the ligand basic amino group during the initial soft deprotonation and the key asymmetric γ-protonation. Remarkably, other coinage metals, that is, Ag and Au, can readily assume the same role as Cu in this asymmetric isomerization chemistry.

This review considers phosphine and N-heterocyclic carbene complexes of gold(I) that are used as (pre)catalysts for a range of reactions in organic synthesis. These are divided according to the structure of the ligand, with the narrative focusing on studies that offer a quantitative comparison between the ligands and readily available or widely used existing systems.

The asymmetric hydroboration of alkenes has proven to be among the most powerful methods for the synthesis of chiral boron compounds. This protocol is well suitable for activated alkenes such as vinylarenes and alkenes bearing directing groups. However, the catalytic enantioselective hydroboration of O-substituted alkenes has remained unprecedented. Here we report a Rh-catalyzed enantioselective hydroboration of silyl enol ethers (SEEs) that utilizes two new chiral phosphine ligands we developed. This approach features mild reaction conditions and a broad substrate scope as well as excellent functional group tolerance, and enables highly efficient preparation of synthetically valuable chiral borylethers.

A phosphine-catalyzed cascade annulation of Morita-Baylis-Hillman (MBH) carbonates and diazenes was achieved, giving tetrahydropyrazole-fused heterocycles bearing two five-membered rings in moderate to excellent yields. The reaction underwent an unprecedented reaction mode of MBH carbonates, in which two molecules of MBH carbonates were fully merged into the ring system.

Nitric oxide (NO) is a key signaling molecule in health and disease. While nitrite acts as a reservoir of NO activity, mechanisms for NO release require further understanding. A series of electronically varied β-diketiminatocopper(II) nitrite complexes [Cu(II)](κ(2)-O(2)N) react with a range of electronically tuned triarylphosphines PAr(Z)(3) that release NO with the formation of O=PAr(Z)(3). Second-order rate constants are largest for electron-poor copper(II) nitrite and electron-rich phosphine pairs. Computational analysis reveals a transition-state structure energetically matched with experimentally determined activation barriers. The production of NO follows a pathway that involves nitrite isomerization at Cu(II) from κ(2)-O(2)N to κ(1)-NO(2) followed by O-atom transfer (OAT) to form O=PAr(Z)(3) and [Cu(I)]-NO that releases NO upon PAr(Z)(3) binding at Cu(I) to form [Cu(I)]-PAr(Z)(3). These findings illustrate important mechanistic considerations involved in NO formation from nitrite via OAT.

Enantioenriched phosphine azoles were synthesized in high yields via palladium-catalyzed asymmetric hydrophosphination with excellent yields and enantioselectivities under mild reaction conditions. One of the phosphine azoles was methylated and complexed to palladium(II) cleanly to give a chiral phosphine-NHC palladium(II) complex with excellent overall conversion. Ministry of Education (MOE) Submitted/Accepted version This research is supported by the Ministry of Education, Singapore, under its Academic Research Fund Tier 1 (2019- T1-001-094).

An interesting remote δ-C 1,6-addition and an isomerization cascade reaction for phosphine-catalyzed activated alkynes have been disclosed. The products featuring a functional diene and a 1,1-diaryl methyl motif have been obtained in moderate to good yields (30-86%) by applying para-quinone methides (p-QMs) and δ-substituted alkynoate with tributylphosphine (PnBu3) catalysis, along with high regioselectivity and stereoselectivity (dr > 20:1). The wide scope of compatible substrates (35 examples), such as indolyl, oxindolyl, ester, and cinnamyl, expand the utility of this methodology. A plausible mechanism and some applications of it have also been presented.

The synthesis and characterization of nickel, cobalt, and iron complexes of the bis(phosphine)carbodicarbene (CDC) ligand 1 is described. The square-planar complexes can be synthesized without the isolation of the deprotonated carbodicarbene ligand, and three different synthetic methods were used to make these first-row transition-metal compounds. The reaction between ligand 1-BPh4 and Ni(COD)2 afforded the compound [(CDC)Ni(η1-C8H13)][BPh4] (2-BPh4) via the insertion of COD into the Ni–H bond produced by cyclometalation. The complexes [(CDC)MCl]+ for nickel and cobalt were synthesized from the reaction of carbodicarbene ligand 1 with NiCl2 or CoCl2 in the presence of triethylamine. For the synthesis of the iron coordination complex of CDC ligand 1, Fe2Mes4 was used to produce [(CDC)Fe-Mes][BPh4] (5), an intermediate-spin Fe(II) compound. Complexes 3–7 were characterized by spectroscopic methods and X-ray single-crystal diffraction analysis.

Metal-organic framework (MOF) materials are intriguing photocatalysts to trigger radical-mediated chemical transformations. We report herein the synthesis and characterization of a series of isomorphic MOFs which show a novel structure, wide visible-light absorption, high chemical stability, and specific redox potential. The prepared MOFs were explored for the photoinduced single-electron oxidation of thiol compounds, generating reactive thiyl radicals to afford thioethers via a convenient thiol-olefin reaction. Importantly, we provide a widely applicable strategy by combing a photoactive MOF with phosphine to modulate the generation of thiyl radical in the reaction, thereby producing a single product of the thioether without the formation of a disulfide byproduct due to the dimerization of thiyl radicals. The photocatalytic reaction takes advantage of this strategy, showing great generality where tens of thiols and olefins have been examined as coupling partners. In addition, the strategy has also been demonstrated to be effective for the reactions catalyzed by other MOFs. Mechanism studies reveal that the selective synthesis of C-S products relies on a synergy between the photoinduced generation of a thiyl radical over the MOF and the in situ cleavage of S-S bond into a S-H bond by phosphine. It is notable that the synthesized MOFs show advanced performance in comparison with classical MOFs. The work not only provides a series of novel MOF photocatalysts that are capable of photoinduced thiol-olefin coupling but also indicates the great potential of MOFs for photochemical transformations mediated by reactive radicals.

The chemistry of discrete molecular chains constituted by metals in low oxidation states, displaying metal-metal proximity and stabilized by suitable metal-bridging, assembling ligands comprising at least one soft donor atom is comprehensively reviewed; complexes with a single (hard or soft) bridging atom (e.g., μ-halide, μ-sulfide, or μ-PR2etc.) as well as "closed" metal arrays (that fall in the realm of cluster chemistry) are excluded. The focus is on transition metal-based systems, with few excursions to cases combining transition and post-transition elements. Most relevant supporting ligands have neutral C, P, O, or S donor (mainly, N-heterocyclic carbene, phosphine, ether, thioether) or anionic donor (mainly phenyl, ylide, silyl, phosphide, thiolate) groups. A supporting-ligand-based classification of the metal chains is introduced, using as the classifying parameter the number of "bites" (i.e., ligand bridges) subtending each intermetallic separation. The ligands are further grouped according to the number of donor atoms interacting with the metal chain (called denticity in the following) and the column of the Periodic Table to which the set of donor atoms belongs (in ascending order). A complementary metal-based compilation of the complexes discussed is also provided in a concise tabular form.

Phosphines were previously unusable as Pummerer-type nucleophiles due to competing redox chemistry with sulfoxides. Here we circumvent this problem to achieve a formal phosphine Pummerer reaction that offers thioalkyl phosphonium salts that, in turn, give rise to diverse vinyl sulfides via Wittig olefinations. Thirty vinyl sulfides are thus prepared from (alkylthioalkyl)triphenyl phosphonium salts and aldehydes. The hydrolysis of these vinyl sulfides offers an efficient and versatile two-step one-carbon homologation of aldehydes to ketones.

Studies into the mechanism of 8-aminoquinoline-directed nickel-catalyzed C(sp3)–H arylation with iodoarenes are described, in an attempt to determine the catalyst resting state and optimize catalytic performance. Paramagnetic complexes are identified that are undergo the key C–H activation step. Hammett analysis using electronically different aryl iodides suggests a concerted oxidative addition mechanism for the C–H functionalization step; DFT calculations were also performed to support this finding. When Na2CO3 is used as the base the rate determination step for C–H functionalization appears to be 8-aminoquinoline deprotonation and binding to Ni. The carbonate anion was also observed to provide a deleterious NMR inactive low-energy off-cycle resting state in catalysis. Replacement of Na2CO3 with NaOtBu not only improved catalysis at milder conditions but also eliminated the need for carboxylic acid and phosphine additives.

A copper-catalyzed difunctional cyano-, thiocyano-, and chlorophosphorylation reaction of alkynes with P(O)-H compounds and coupling partners (TBACN, TMSNCS, TMSCl) is described. The reaction introduces versatile groups (-P(O)R2 and -CN, -SCN, or -Cl) to form tri- and tetrasubstituted alkenyl phosphine oxides/phosphonates regio- and stereoselectively.

The bidentate phosphine ligand 1,2-bis(di-tert-butylphosphinomethyl)benzene (1,2-DTBPMB) has been reported over the years as being one of, if not the, best ligands for achieving the alkoxycarbonylation of various unsaturated compounds. Bonded to palladium, the ligand provides the basis for the first step in the commercial (Alpha) production of methyl methacrylate as well as very high selectivity to linear esters and acids from terminal or internal double bonds. The present review is an overview covering the literature dealing with the 1,2-DTBPMB ligand: from its first reference, its catalysis, including the alkoxycarbonylation reaction and its mechanism, its isomerization abilities including the highly selective isomerizing methoxycarbonylation, other reactions such as cross-coupling, recycling approaches, and the development of improved, modified ligands, in which some tert-butyl ligands are replaced by 2-pyridyl moieties and which show exceptional rates for carbonylation reactions at low temperatures.

A new gold cluster compound [Au23(NHCptol)6(C≡CPh)9]2+ (NHCptol = 1,3-di(para-methylbenzyl)benzimidazolin-2-ylidene) (Au23NHCptol) was synthesized, and its geometric and electronic structures were ...

We report an easily prepared and bench-stable mononuclear Pd(0) source stabilized by a chelating N,N′-diaryldiazabutadiene ligand and maleic anhydride: DMPDAB–Pd–MAH. Phosphine ligands of all types...

In the presence of [p-cymene)RuCl2]2, (E)-configured alkenyl bromides couple with aromatic carboxylates to form ortho-vinylbenzoic acids. This C-H vinylation proceeds in high yields without any activating phosphine ligands and has an excellent functional group tolerance. Starting from commonly available (E/Z )-mixtures of alkenyl bromides, (E)-configured vinyl arenes or dienes are formed exclusively. Mechanistic studies show that this selectivity is achieved because the (E)-configured alkenyl bromides undergo a smooth coupling, whereas the (Z)-isomers are rapidly eliminated with the formation of alkynes.