Elimination Products Research Articles

Dinuclear Cobalt(II) Bis-Dipyrromethane Complexes: Synthesis via Divergent Transmetalation Reactions.

A bis-dipyrromethane ligand, 4,4'-bis(1,1-bis(3,5-dimethyl-1H-pyrrol-2-yl)ethyl)-1,1'-biphenyl, [H4-MeBDPM-BPh] (1), is synthesized via acid-catalyzed electrophilic aromatic substitution of 2,4-dimethylpyrrole with 4,4'-diacetylbiphenyl. Subsequent deprotonation of 1 with n-BuLi yields the corresponding Li-salt [Li4-MeBDPM-BPh] (2). Transmetalation involving 2 and either CoCl2 or [Co(HMDS)2] (HMDS = -N(Si(CH3)3)2) results in dinuclear Co(II) complexes. In the case of CoCl2, the formation of the ate-complex 2[Li(THF)4][(MeBDPM-BPh){Co(μ-Cl)2Li(THF)2}2] (3) is observed where each metal center occupies a tetrahedral geometry with noninteracting metal centers. However, when utilizing [Co(HMDS)2], the dinuclear complex 2[Li(THF)4][(MeBDPM-BPh){Co(HMDS)}2] (4) is obtained with the formation of LiHMDS as the product of elimination. The Co metal centers of complex 4 are both three-coordinate and trigonal planar. Displacement of LiHMDS from 4 readily occurs upon treatment with the ylide base, H2CPPh3, yielding the neutral complex [(MeBDPM-BPh){Co(H2CPPh3)2}2] (5). At room temperature, complexes 3-5 have magnetically noninteracting metal centers with S = 3/2 spin states.

Rebuttal to the article Pathological crystal structures.

A section in the Acta Crystallographica Section C article by Raymond & Girolami [Acta Cryst. (2023), C79, 445-455] stated that the product of the reaction of [(Cp*Rh)2(μ-OH)3]+ (Cp* is 1,2,3,4,5-pentamethylcyclopentadiene) with 1-methylthymine (1-MT) at pH 10 and 60 °C, to synthesize the anionic component [RhI(η1-N3-1-MT)2]-, was not an RhI complex, but rather an AgI complex, due to the use of silver triflate (AgOTf) to remove Cl- from [Cp*RhCl2]2 to synthesize [Cp*Rh(H2O)3](OTf)2, a water-soluble crystalline complex. We will clearly show that this premise, as stated, is invalid, while the authors have simply avoided several important facts, including that Cp*OH, a reductive elimination product, at pH 10 and 60 °C, was unequivocally identified, thus leading to the RhI anionic component [RhI(η1-N3-1-MT)2]-. More importantly, AgOH, from the reaction of NaOH at pH 10 with any potentially remaining AgOTf, after the AgCl was filtered off, would be insoluble in water. Furthermore, a control experiment with the inorganic complex Rh(OH)3, reacting with 1-methylthymine at pH 10, provided no product, and this bodes well for a similar fate with AgOTf and 1-methylthymine, i.e. at pH 10, AgOTf would again be converted to the water-insoluble AgOH; therefore, no reaction would occur! Finally, a 1H NMR spectroscopy experiment was carried out with synthesized and crystallized [Cp*Rh(H2O)3](OTf)2 in D2O at various pD values; at pD 8.65 no reaction took place, while at pD 13.6, and at 60 °C for 2 h, a reductive elimination reaction caused the precipitation of Cp*OH. The subsequent 1H NMR spectrum clearly demonstrated, in the absence of any AgI complexes, that the solution structure and the X-ray crystals in D2O were similar. A postulated mechanism for this novel anionic component structure, as published previously [Smith et al. (2014). Organometallics, 33, 2389-2404], will be presented, along with the experimental data, to insure the credibility of our results. We will also answer the comments in the response of Drs Raymond and Girolami to this rebuttal.

High Selectivity in Csp2-Csp2 versus Csp3-O Reductive Elimination from Cycloplatinated(IV) Complexes.

The cycloplatinated(IV) complexes trans-[Pt(p-MeC6H4)(C∧N)(OAc)2(H2O)] (C∧N = benzo[h]quinolate, bhq, 2a, and 2-phenylpyridinate, ppy, 2b) were prepared by reacting the corresponding [Pt(p-MeC6H4)(C∧N)(SMe2)] precursors with PhI(OAc)2 through an oxidative addition (OA) reaction. Thermolysis of 2a at 65 °C generates cis-[Pt(κ1N-10-(p-MeC6H4)-bhq)(OAc)2(H2O)], 3a, which is the product of a Csp2Ar-Csp2bhq reductive elimination (RE). The observed coupling reaction is significantly different from the previously reported analogous thermolysis of trans-[PtMe(C∧N)(OAc)2(H2O)] (C∧N = bhq, 2c, and ppy, 2d) that selectively releases Me-OAc (C-O RE). The density functional theory (DFT) calculations and experimental observations reveal that the Csp2Ar-Csp2bhq coupling reaction occurs through the dissociation of a coordinated water ligand. This in turn is followed by the concomitant bond forming and bond breaking process via a three-center ring transition state, in contrast to the Csp3Me-OAc coupling, which had taken place by an outer sphere SN2 type RE reaction in methyl complexes.

Efficient CO Oxidative Coupling to Dimethyl Oxalate over the Pd/Al2O3 Nanocatalyst with the Assistance of Co Doping

AbstractCO oxidative coupling to dimethyl oxalate (DMO) is an important approach for the product of ethylene glycol and CO elimination. In this work, the Co doped Pd/Al2O3 nanocatalyst was highly effective for CO oxidative coupling and enhanced remarkably CO conversion and the formation of DMO. The maximum DMO STY reached 1082 g L−1 h−1 over the Pd/Al2O3@1/20Co catalyst at 130 °C for 2 h under the space velocity of 3000 h−1, which is two times higher than that over the Pd/Al2O3 catalyst. The Co modification and its influence on the structure of the Pd/Al2O3 catalyst were also studied systematically by XRD, TEM, CO‐TPD, N2 physical adsorption and XPS techniques. An appropriate Co doing was confirmed to promote distinctly the generation of smaller Pd particles and the adjustment of the adsorption or activation of CO over the catalyst. A positive interaction between Pd nanoparticles and the modulated support with Co doping was demonstrated and favored the enhanced activity of the catalyst for the reaction.

Strategies to Cope with Inferior Long-Term Photostability of Bentonite Polyolefin Nanocomposites.

This study provides insight into the causes of inferior long-term stability of nanocomposites based on organic layered silicates (OLSs) used for cable mantles. A hierarchy was established by analyzing bentonite products and their respective polyolefin nanocomposites. Thermogravimetric analysis (TGA), X-ray diffraction (XRD), gas adsorption, energy-dispersive spectroscopy (SEM-EDX), and infrared spectroscopy (IR) provided evidence for the adsorption of stabilizers onto the filler surface and thus their reduction in activity, promoting polymer oxidation. This behavior corresponds to the specific surface area of the incorporated OLS. Therefore, it can be stated that gas adsorption and XRD are especially useful for the evaluation of long-term photostability. It was revealed that photocatalytically active iron is of secondary importance since iron-rich bentonites still formed the most stable nanocomposite. This also applies to the Hofmann elimination products of the modifying agent, where higher contents do not accelerate the degradation process. No elimination products could be traced within the composites. Due to the polymer-filler interface being essential for long-term photostability, prior analysis of the filler surface properties can be used to estimate the stability of the respective nanocomposite as a rationale for product selection in the early stages of development. The reasons identified in this work for decreasing the long-term photostability of OLS nanocomposites compared with unfilled formulations is an important step toward increasing their stability.

Steric Perturbation of the Grob-like Final Step of Ethylene-Forming Enzyme Enables 3-Hydroxypropionate and Propylene Production.

Ethylene-forming enzyme (EFE) is an iron(II)-dependent dioxygenase that fragments 2-oxoglutarate (2OG) to ethylene (from C3 and C4) and 3 equivs of carbon dioxide (from C1, C2, and C5). This major ethylene-forming pathway requires l-arginine as the effector and competes with a minor pathway that merely decarboxylates 2OG to succinate as it oxidatively fragments l-arginine. We previously proposed that ethylene forms in a polar-concerted (Grob-like) fragmentation of a (2-carboxyethyl)carbonatoiron(II) intermediate, formed by the coupling of a C3-C5-derived propion-3-yl radical to a C1-derived carbonate coordinated to the Fe(III) cofactor. Replacement of one or both C4 hydrogens of 2OG by fluorine, methyl, or hydroxyl favored the elimination products 2-(F1-2/Me/OH)-3-hydroxypropionate and CO2 over the expected olefin or carbonyl products, implying strict stereoelectronic requirements in the final step, as is known for Grob fragmentations. Here, we substituted active-site residues expected to interact sterically with the proposed Grob intermediate, aiming to disrupt or enable the antiperiplanar disposition of the carboxylate electrofuge and carbonate nucleofuge required for concerted fragmentation. The bulk-increasing A198L substitution barely affects the first partition between the major and minor pathways but then, as intended, markedly diminishes ethylene production in favor of 3-hydroxypropionate. Conversely, the bulk-diminishing L206V substitution enables propylene formation from (4R)-methyl-2OG, presumably by allowing the otherwise sterically disfavored antiperiplanar conformation of the Grob intermediate bearing the extra methyl group. The results provide additional evidence for a polar-concerted ethylene-yielding step and thus for the proposed radical-polar crossover via substrate-radical coupling to the Fe(III)-coordinated carbonate.

Chemoselective Intramolecular Morita-Baylis-Hillman Reaction; Acrylamide and Ketone as Sluggish Reacting Partners on a Labile Framework.

Chemoselectivity is an important issue frequently encountered while working over labile precursors. Carbonyl compounds with a heteroatom at the β carbon are sensitive precursors because they are prone to elimination under different conditions. Morita-Baylis-Hillman (MBH) reaction, although a widespread method for C-C bond formation, has its own limitations. Acrylamide and ketone are such limitations of the MBH reaction. Using them together for an intramolecular MBH (IMBH) reaction on a labile framework prone to elimination is a significant 2-fold synthetic challenge. A highly chemoselective IMBH reaction on such precursors has been established using 1,4-diazabicyclo[2.2.2]octane (DABCO) as a promoter. The protocol leads to quick access to a diversely substituted and functionalized piperidone framework in high yields. Various substitution patterns in the form of 34 successful examples have been studied. A diastereoselective version and tolerance to various functional and protecting groups are the added advantages of the developed methodology. A tertiary carbon at the β position of ketone, however, led to complete reversal of selectivity and gave only the elimination product. Control experiments toward a better understanding of the substitution pattern, role of catalyst, and mechanistic study have been carried out. As an application of the IMBH adduct, a one-step allylic rearrangement for the dihydropyridone framework has also been demonstrated.

Kumada-Tamao-Corriu Type Reaction of Aromatic Bromo- and Iodoamines with Grignard Reagents.

The first example of the Kumada-Tamao-Corriu type reaction of unprotected bromoanilines with Grignard reagents is described. The method uses a palladium source and a newly designed Buchwald-type ligand as the catalytic system. Secondary and tertiary bromo- and iodoamines were also successfully coupled to alkyl Grignard reagents. The products of the competitive β-hydride elimination reaction were successfully reduced using a highly efficient electron-deficient phosphine ligand (BPhos). Mechanistic considerations allowed us to establish that the less electron-rich phosphine ligands stabilize the transition state much better than the electron-rich ones; hence, they increase the reaction yield and reduce the amount of β-hydride elimination products. The developed method proved to be tolerant of many functional groups and can be applied to many different aromatic bromo- and iodoamines. Multigram synthesis of p-toluidine from 4-bromoaniline was achieved with a palladium catalyst loading of only 0.03 mol%.

Enzymatic β-elimination in natural product O- and C-glycoside deglycosylation

Biological degradation of natural product glycosides involves, alongside hydrolysis, β-elimination for glycosidic bond cleavage. Here, we discover an O-glycoside β-eliminase (OGE) from Agrobacterium tumefaciens that converts the C3-oxidized O-β-d-glucoside of phloretin (a plant-derived flavonoid) into the aglycone and the 2-hydroxy-3-keto-glycal elimination product. While unrelated in sequence, OGE is structurally homologous to, and shows effectively the same Mn2+ active site as, the C-glycoside deglycosylating enzyme (CGE) from a human intestinal bacterium implicated in β-elimination of 3-keto C-β-d-glucosides. We show that CGE catalyzes β-elimination of 3-keto O- and C-β-d-glucosides while OGE is specific for the O-glycoside substrate. Substrate comparisons and mutagenesis for CGE uncover positioning of aglycone for protonic assistance by the enzyme as critically important for C-glycoside cleavage. Collectively, our study suggests convergent evolution of active site for β-elimination of 3-keto O-β-d-glucosides. C-Glycoside cleavage is a specialized feature of this active site which is elicited by substrate through finely tuned enzyme-aglycone interactions.

A [CoSiH2] Silylene Synthon Provides Modular Access to Homo- and Heterobimetallic [Co═Si═M] (M = Co, Fe) Silicide Complexes.

Base-stabilized [BP3iPr](H)2CoSiH2(DMAP) (1, [BP3iPr] = PhB(CH2PiPr2)3-; DMAP = 4-dimethylaminopyridine) is a rare instance of a synthon for the simplest "parent" silylene complex (LM═SiH2). Complex 1 was accessed in high yields via double Si-H bond activation in SiH4 by [BP3iPr]Co(DMAP), and in solution, it undergoes rapid exchange between bound and free DMAP by an associative mechanism (as determined by variable-temperature 1H NMR dynamic studies). The DMAP ligand of 1 is readily displaced by metal-based fragments that bind silicon and cleave the Si-H bonds of the SiH2 moiety to produce bimetallic [Co═Si═M] (M = Co, Fe) molecular silicides. Thus, treatment of 1 with 0.5 equiv of (LCoI)2(μ-N2) (L = a tripodal ligand) resulted in the spontaneous formation of [BP3iPr](H)2Co═Si═Co(H)2L (L = [BP2tBuPz], PhB(CH2PtBu2)2(pyrazolyl)- (3); Tp″, HB(3,5-diisopropylpyrazolyl)3- (4)) with the concomitant release of DMAP. The symmetrical silicide [BP3iPr](H)2Co═Si═Co(H)2[BP3iPr] (5) was prepared by treatment of a mixture of 1 and [BP3iPr]Co(DMAP) with 2 equiv of Ph3B, which in this case is required to sequester DMAP as the elimination product Ph3B-DMAP. A heterobimetallic silicide, [BP3iPr](H)2Co═Si═Fe(H)2[SiP3iPr] (7; [SiP3iPr] = PhSi(CH2PiPr2)3), was obtained via in situ KC8 reduction of [SiP3iPr]FeCl and subsequent addition of 1 and Ph3B. These transformations involving a metal-SiH2 derivative demonstrate a fundamentally new type of reactivity for silylene complexes and provide a unique synthetic method for construction of molecular silicide complexes.

Montmorillonite Catalyzed Synthesis of Novel Steroid Dimers.

The reactions of sterols (androst-5-en-3β-ol-17-one, diosgenin, and cholesterol) and their tosylates with hydroquinone aimed at the synthesis of O,O-1,4-phenylene-linked steroid dimers were studied. The reaction course strongly depended on the conditions used. The study has shown that the major reaction products are the elimination products and unusual steroid dimers resulting from the nucleophilic attack of the hydroquinone C2 carbon atom on the steroid C3 position, followed by an intramolecular addition to the C5-C6 double bond. A different reaction course was observed when montmorillonite K10 was used as a catalyst. The reaction of androst-5-en-3β-ol-17-one under the promotion of this catalyst afforded the O,O-1,4-phenylene-linked steroid dimer in addition to the disteroidal ether. The formation of the latter compound was suppressed by using 3-tosylate as a substrate instead of the free sterol. The reactions of androst-5-en-3β-ol-17-one tosylate and cholesteryl tosylate with hydroquinone catalyzed by montmorillonite K10 carried out under optimized conditions afforded the desired dimers in 31% and 67% yield, respectively.

Second‐Generation Total Synthesis of the Pigment Aurantricholone

AbstractOur first total synthesis of aurantricholone established its benzotropolone core by the ring‐enlargement of a tetralone. Here we describe another total synthesis of aurantricholone. It reaches the benzotropolone core from a known olefin metathesis product via an equally known dibromide, both of which contain a ketoketal moiety. The next transformation ‐ step 9 overall ‐ engaged this motif in a β‐elimination of ROH rather than in a hydrolysis under the forcing acidic conditions indispensable in all prior benzotropolone preparations from such an intermediate. In step 10, the Csp2−Br bonds of the elimination product underwent two doubly Z‐selective Suzuki couplings with a boronylated O‐methyl 4‐methylidenetetronate. This gave penta(O‐methyl)aurantricholone. Its NMR shifts matched essentially those of a derivative of natural aurantricholone by Steglich et al. Three O−Me bonds were cleaved with BBr3/CH2Cl2 (step 11) and two O−Me bonds with LiBr/DMF (step 12). A 1 : 3 co‐crystal of aurantricholone and DMSO allowed for an X‐ray structure analysis.

Features of (Benzo)Imidazo[2,1-b][1,3]thiazine Mezylates Reaction with Nucleophilic Reagents

Peculiarities of the course of the methanesulfo-derivatives of (benzo)imidazo[2,1-b][1,3]thiazines reac-tions with a number of nucleophilic reagents were studied. It was determined that they react nonselectively with potassium thiocyanate to form a mixture of thio- and isothiocyanate derivatives. When interacting with sodium azide, nucleophilic substitution competes with an elimination reaction. The latter is dominant in the reaction with sodium cyanide. The spatial structure of one of the isomer elimination products, 4H-benzo[4,5]imidazo[2,1-b][1,3] thiazine, was established by X-ray structural analysis.

Boosting CO2 hydrogenation of Fe-based monolithic catalysts via 3D printing technology-induced heat/mass-transfer enhancements

The direct transformation of CO2 into valuable chemicals with the aid of sustainable energy-generated H2 has attracted enormous interest owing to the integrated functions of carbon elimination and non-fossil fuel-derived products supply. As one of the most promising catalysts for CO2 hydrogenation, the chemical properties of Fe-based catalysts, such as electronic structure and coordination environment, have been widely studied. However, the mass/heat transfer effects in Fe-based catalysts are also crucial to the targeted product selectivity and catalytic stability, but have been rarely investigated due to the lack of facile fabrication protocols. Herein, we precisely fabricate and tailor the architecture of the Fe-based monolithic catalysts by a direct ink writing (DIW)-type three-dimensional (3D) printing technology under the guidance of the computationally controlled printing procedure. The Fe-based monolithic catalyst with spiral-type architecture delivers extremely high light olefins selectivity (52.6%) and space time yield (STY, 451.8 gCH2 kgcat−1 h−1) from CO2 hydrogenation. Based on the mass-transfer simulation, the spiral-structured channels in the Fe-based monolithic catalyst lower the coverage of intermediates and products on the catalytic interface due to the optimal mass-transfer effect, thus maximizing the utilization of active sites and timely terminating the carbon-chain growth. More in-depth, the density functional theoretical (DFT) simulations verify that the relatively electron-rich catalytic interface with low intermediate coverage could facilitate the desorption of olefins and decelerate the C-C coupling step, which synergistically guarantee the enhanced light olefins synthesis performance. Furthermore, the enhanced heat-transfer effect endowed by the 3D architecture prolongs the life-time of catalyst by avoiding undesirable active site aggregation and carbon deposition. The powerful strategy for catalyst fabrication not only provides a new concept of regulating the CO2 hydrogenation performance of Fe-based catalysts but also holds a great promise to spread into other catalytic systems for targeted synthesis.

Co3O4[sbnd]CeO2 heterogenous interfaces as a high-efficient catalyst for soot oxidation

Developing advanced catalysts for efficiently eliminating soot particles could be significant for achieving the goal of Euro 6 and China VIB. Co3O4/CeO2 nanocomposites containing Co3O4CeO2 interfaces are considered as efficient catalysts for removing soot particles, while the role of Co3O4CeO2 interfaces is still unclear. In this study, Co3O4/CeO2 nanocomposites with different contents of Co3O4CeO2 interfaces were prepared to investigate the role of Co3O4CeO2 interfaces in promoting soot oxidation. Experimental results show that Co3O4CeO2 interfaces can efficiently eliminate soot nanoparticles, while the content of which weakly influences the elimination temperatures and products selectivity. It was found that the reaction dynamic and intrinsic activity are found to change with the content of Co3O4CeO2 interfaces. Further investigations demonstrate that a few amounts of Co3O4CeO2 interfaces can significantly increase the O2-preferred active sites, but not significantly enhance the movability of active oxygen species and the activation of NO. Increasing Co3O4CeO2 interfaces can enrich the NO-preferred active sites and enhance the movability of active oxidative species. As a result, rich Co3O4CeO2 interfaces lead to low soot-eliminating temperatures (T50: 407 °C) and high intrinsic activity (TOF: 0.99 h−1), while a few amounts of Co3O4CeO2 interfaces perform low soot-eliminating temperatures (T50: 403 °C) with low intrinsic activity (TOF: 0.68 h−1). Results of this work might be meaningful in designing robust nanomaterials with heterogenous interfaces.

Quantitative characterizations of the cholesterol-related pathways in the retina and brain of hamsters

The retina and brain are separated from the systemic circulation by the anatomical barriers, which are permeable (the outer blood-retinal barrier) and impermeable (the blood-brain and inner blood-retina barriers) to cholesterol. Herein we investigated whether whole-body cholesterol maintenance affects cholesterol homeostasis in the retina and brain. We used hamsters, whose whole-body cholesterol handling is more similar to those in humans than in mice, and conducted separate administrations of deuterated water and deuterated cholesterol. We assessed the quantitative significance of the retinal and brain pathways of cholesterol input and compared the results with those from our previous studies in mice. The utility of the measurements in the plasma of deuterated 24-hydroxycholesterol, the major cholesterol elimination product from the brain, was investigated as well. We established that despite a sevenfold higher serum LDL to HDL ratio and other cholesterol-related differences, in situ biosynthesis remained the major source of cholesterol for hamster retina, although its quantitative significance was reduced to 53% as compared to 72%–78% in the mouse retina. In the brain, the principal pathway of cholesterol input was also the same, in situ biosynthesis, accounting for 94% of the total brain cholesterol input (96% in mice); the interspecies differences pertained to the absolute rates of the total cholesterol input and turnover. We documented the correlations between deuterium enrichments of the brain 24-hydroxycholesterol, brain cholesterol, and plasma 24-hydroxycholesterol, which suggested that deuterium enrichment of plasma 24-hydroxycholesteol could be an in vivo marker of cholesterol elimination and turnover in the brain.

Accelerating SN2 nucleophilic fluorination of primary alkyl bromide using an 18-crown-6 and fluorinated bulky alcohol phase transfer system

A new phase transfer system for nucleophilic fluorination of alkyl halides with potassium fluoride, based on the combination of 18-crown-6 and the bulky fluorinated alcohol 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, was found to be very effective. A primary alkyl bromide was fluorinated in 24 h of reaction time with a mild temperature of 82 °C using acetonitrile solvent, obtaining 80% yield and only a trace of elimination product. The rational choice of this alcohol was based on a free energy profile of a reaction model including the solubilization of the KF salt and on the theoretical calculations of the stability of the KF(18-crown-6)(alcohol) complexes. The fluorinated bulky alcohol leads to a substantial increase in the concentration of KF complexed with 18-crown-6, which compensates for the decreased reactivity of the solubilized complex. The present study shows the importance of the modulation of the hydrogen bonding strength to obtain the rate acceleration effect.

A Computational Study on the Radical Cascade Cyclization Mechanism of Synthesis of Benzo[b]oxepinones and Chromanes

AbstractA computational study on the reaction mechanism of the effective synthesis of sulfonated benzo[b]oxepinones and chromanes by radical cascade cyclization is carried out employing the density functional theory (DFT). Based on our computations, the rate‐determining step is the formation of arylsulfonyl radical for the reaction scheme. Our calculations show that the reaction of 1,8‐ and 1,7‐enynes with arylsulfonyl radical proceeds by forming more thermodynamically stable intermediates. Therefore, 1,8‐enynes prefer 7‐exo‐trig cyclization, while 1,7‐enynes prefer 6‐exo‐trig cyclization. Our computations are consistent with experimental results of the radical cascade cyclization of 1,8‐ and 1,7‐enynes. Moreover, our computations show that if the reaction is carried out in a proton‐free solvent, the elimination product can be obtained from the cascade radical cyclization of the 1,7‐enyne.

Coumarin C-H Functionalization by Mn(I) Carbonyls: Mechanistic Insight by Ultra-Fast IR Spectroscopic Analysis.

Mn(I) C-H functionalization of coumarins provides a versatile and practical method for the rapid assembly of fused polycyclic pyridinium-containing coumarins in a regioselective manner. The synthetic strategy enables application of bench-stable organomanganese reagents in both photochemical- and thermal-promoted reactions. The cyclomanganated intermediates, and global reaction system, provide an ideal testing ground for structural characterization of the active Mn(I) carbonyl-containing species, including transient species observable by ultra-fast time-resolved spectroscopic methods. The thermodynamic reductive elimination product, solely encountered from reaction between alkynes and air-stable organometallic cyclomanganated coumarins, has enabled characterization of a critical seven-membered Mn(I) intermediate, detected by time-resolved infrared spectroscopy, enabling the elucidation of the temporal profile of key steps in the reductive elimination pathway. Quantitative data are provided. Manganated polycyclic products are readily decomplexed by AgBF4 , opening-up an efficient route to the formation of π-extended hybrid coumarin-pyridinium compounds.

How Topological Differences between Two Oxide Surfaces Determine Selectivity—The Case of the Dehydra-Decyclization of Tetrahydrofuran

Production of butadiene from biomass-based tetrahydrofuran (THF) is explored as an alternative to the existing petroleum-based processes. Metal oxide catalysts have been shown to exhibit varying product selectivities when reacted with THF. Among those oxides, ZrO2 showed the highest selectivity for butadiene. In contrast, Al2O3 showed the highest selectivity for the competing retro-Prins products, C3H6 and HCHO. The reasons behind the varying selectivity across oxides are unclear. In this work, we employ periodic density functional theory and mean-field microkinetic modeling to investigate the mechanism of the reaction of THF to butadiene and retro-Prins products on t-ZrO2 (101) (dry and hydrous) and on γ-Al2O3 (110). Our simulations reproduce the experimental selectivity trends. High selectivity for butadiene is promoted by the presence of neighboring Lewis acid metal sites that facilitate E1cB hydroxyl elimination from a 3-butenoxide intermediate; on hydrous Al2O3; where such neighboring Lewis acid centers are not available, the butenoxide undergoes E2 elimination and retro-Prins products ensue. The THF ring opening is rate-determining on ZrO2, whereas the γ-proton elimination that yields the 3-butenoxide intermediate is rate controlling on hydroxylated Al2O3. We conclude that the local topology around the active site greatly influences the mechanism and selectivity.