Inexpensive and bench stable diarylmethylium tetrafluoroborates as organocatalysts in the light mediated hydrosulfonylation of unactivated alkenes.

In this paper, we present the synthetic potential of diarylmethylium tetrafluoroborates as catalysts for the visible light promoted hydrosulfonylation of unactivated alkenes. For the first time, these salts, which are bench stable and easily preparable on a multi-gram scale, were employed as organocatalysts. Interestingly, a catalyst loading of only 1 mol% allowed sulfone products to be efficiently obtained from good-to-excellent yields with high functional-group tolerance and scalability up to 15 mmol of alkene. The mechanistic study, both experimental and computational, presented here, revealed an alternative mechanism for the formation of the key sulfonyl radical. Indeed, the photoactive species was proved not to be the diarylcarbenium salt itself, but two intermediates, a stable S-C adduct and an ion couple, that were formed after its interaction with sodium benzenesulfinate. Upon absorbing light, the ion couple could reach an excited state with a charge-transfer character which gave the fundamental sulfonyl radical. A PCET (proton-coupled electron transfer) closes the catalytic cycle reforming the diarylcarbenium salt.

Photoinduced Chloroamination Cyclization Cascade with N-Chlorosuccinimide: From N-(Allenyl)sulfonylamides to 2-(1-Chlorovinyl)pyrrolidines.

Here, we present an intriguing photoinduced chloroamination cyclization of allenes bearing a tethered sulfonylamido group to afford 2-(1-chlorovinyl)pyrrolidines and related heterocycles in the presence of N-chlorosuccinimide (NCS) as the chlorine source. An in depth experimental and computational mechanistic study revealed the existence of multiple reaction pathways leading to a common nitrogen centered radical (NCR). This key NCR can be, in fact, originated from (a) the oxidation of the deprotonated allene by the photoexcited state of the Ru-catalyst and (b) the photodissociation of the in situ formed N-chloroallene. The NCR formation triggers an intramolecular cyclization to a highly reactive pyrrolidine vinyl radical, which upon chlorination delivers the final product. Thus, NCS plays a dual role, serving both as an activator of the sulfonamido functionality and as the chlorinating agent.

Ullmann homocoupling of arenediazonium salts in a deep eutectic solvent. Synthetic and mechanistic aspects.

A deep eutectic solvent (DES) based on glycerol and KF is successfully exploited as a solvent medium in Ullmann homocoupling of arenediazonium salts. The reactions were carried out in mild conditions and target products were obtained in fairly good yields. A computational study is presented aiming to understand the reaction mechanism and Raman spectroscopy is employed as an experimental tool to support it.

Copper-Free Halodediazoniation of Arenediazonium Tetrafluoroborates in Deep Eutectic Solvents-like Mixtures.

Deep Eutectic Solvent (DES)-like mixtures, based on glycerol and different halide organic and inorganic salts, are successfully exploited as new media in copper-free halodediazoniation of arenediazonium salts. The reactions are carried out in absence of metal-based catalysts, at room temperature and in a short time. Pure target products are obtained without the need for chromatographic separation. The solvents are fully characterized, and a computational study is presented aiming to understand the reaction mechanism.

Visible Light Mediated Photocatalytic N-Radical Cascade Reactivity of γ,δ-Unsaturated N-Arylsulfonylhydrazones: A General Approach to Structurally Diverse Tetrahydropyridazines.

Tetrahydropyridazines are of particular interest for their versatility as intermediates in organic synthesis and display pharmacological activity in several domains. Here, we describe the photocatalytic synthesis of different tetrahydropyridazines starting from γ,δ-unsaturated N-arylsulfonylhydrazones. Simple structural changes of substrates result into three different pathways beginning from a common N-hydrazonyl radical, which evolves through a domino carboamination/dearomatization, a HAT process, or a photoinduced radical Smiles rearrangement to afford diverse tetrahydropyridazines. All reactions are carried out in very mild conditions, and the quite inexpensive [Ru(bpy)3]Cl2 is used as the catalyst. Preliminary mechanism studies are presented, among them luminescence and electrochemical characterization of the involved species. Computational studies allow to rationalize the mechanism in accord with the experimental findings.

Experimental and theoretical study of the fluorescence emission of ferulic acid: Possible insights into the fluorescence properties of humic substances.

Ferulic acid ((E)-3-(4-hydroxy-3-methoxy-phenyl)prop-2-enoic acid, hereinafter FA) is a building block of plant cell walls that is commonly found in lignocellulose. As such, it is a potential component of humic substances produced by microbial degradation of plant spoils. The fluorescence excitation-emission matrix spectra of FA have an interesting humic-like shape, with bands that can be assimilated to the A and C regions of humic substances. Therefore, the study of FA photoluminescence might provide interesting insight into the still unknown processes that lay behind the fluorescence properties of humic compounds. FA is a weak diprotic acid that occurs in three different forms in aqueous solution (neutral H2FA, singly deprotonated HFA- and doubly deprotonated FA2-), which have slightly different absorption and emission properties. The "A-like" fluorescence emission of the FA species is accounted for by excitation from the ground singlet state S0 to singlet excited states higher than the first (S4 for H2FA, S5 for HFA-, and a state higher than S2 for FA2-), followed by radiationless deactivation to the first excited singlet state (S1), and by fluorescence emission according to the S1 → S0 transition. In contrast, the "C-like" emission is mainly caused by S0 → S1 excitation combined with S1 → S0 emission, but there is also a minor contribution from the S0 → S2 excitation that becomes significant for HFA-. The uneven variations with pH of the wavelengths of the maximum FA radiation absorption and fluorescence emission can be rationalised in the framework of the energy levels of the frontier (HOMO and LUMO) molecular orbitals of the different FA species. These levels are affected by charge interaction between the relevant electrons and the neutral (protonated) or negative (deprotonated) groups of each species.

Aerobic CuCl2-Catalyzed Dehydrogenative Cross-Coupling of Tertiary Amines. A Combined Computational and Experimental Study.

The generation of an iminium from amines is a way to functionalize the α carbon by coupling reactions. The reaction mechanism of the conversion of tertiary amines to iminium with CuCl2(H2O)2 as catalyst in aerobic conditions has been computationally and experimentally studied in this work. This process is initiated by the oxidation of the amine to a radical cation dichlorocuprate through the reduction of CuII to CuI. Then, the iminium dichlorocuprate is generated from the radical-ion through a hydrogen-transfer. The H atom can be accepted by molecular oxygen or by a second molecule of catalyst (in anaerobic conditions). Therefore, O2 also assumes the important role of acceptor along with that of regenerator of the catalyst. The experimental study confirmed the computational study and lead to the synthesis of four new molecules from the cross-coupling of N, N-diethyl- and N, N-diisoproylaniline with nitromethane and dimethylmalonate.

Evidence of an Important Role of Photochemistry in the Attenuation of the Secondary Contaminant 3,4-Dichloroaniline in Paddy Water.

The secondary pollutant 3,4-dichloroaniline (DCA) is produced by the biological degradation of several herbicides, including propanil in paddy fields. The enzymatic hydrolysis of propanil yields DCA with almost quantitative yield. DCA undergoes rather fast photodegradation in paddy water, mostly by direct photolysis. An exception might be represented by the cases (rather rare in paddies) of quite high nitrate concentration (around 50 mg of NO3- L-1), when DCA degradation by CO3•- would play a comparable role to that by direct photolysis. The experimentally measured photoreactivity parameters were used as input data for a photochemical model, which predicted a DCA lifetime of 0.5-1 days in sunlit paddy fields in late May, when propanil is usually applied. The model predictions compare remarkably well with the DCA attenuation data reported in field studies, carried out in paddies in temperate regions. Moreover, a consecutive reaction model based on typical biological (propanil) and photochemical (DCA) lifetimes reproduced quite well the time trends of both compounds in paddies, as reported in the literature. These successful comparisons suggest that photodegradation in general, and direct photolysis in particular, may play a key role in DCA attenuation in paddy water.

The nature of the light absorption and emission transitions of 4-hydroxybenzophenone in different solvents. A combined computational and experimental study.

The photophysics and photochemistry of 4-hydroxybenzophenone (4HOBP) are interesting because they can give some insight into the behavior of humic material. Here we show that 4HOBP has a number of fluorescence peaks: (i) an intense one at excitation/emission wavelengths Ex/Em ∼ 200-230/280-370 nm, likely due to an excitation transition from S0 to S5 or S6, followed by S2 → S0 in emission (Sn denotes the singlet states of 4HOBP); (ii) a minor peak at Ex/Em ∼ 270-300/320-360 nm (S0 → S2 in absorption and S2 → S0 in emission), and (iii) very interesting signals in the typical emission region of humic substances, most notably at Ex/Em ∼ 200-220/400-500 nm and Ex/Em ∼ 260-280/400-470 nm (in both cases the emission corresponded to an S1 → S0 transition). The peak (i) (Ex/Em ∼ 200-230/280-370 nm) is quite intense at low 4HOBP concentration values, but it undergoes an effective inner-filter phenomenon. Remarkably, 4HOBP shows fluorescence peaks that arise from S2 → S0 transitions and that do not follow Kasha's rule. Fluorescence is observed in aprotic or poorly protic solvents, and to a lesser extent in aqueous solution. The excited states of 4HOBP, and most notably 4HOBP-S1, are much stronger acids than 4HOBP-S0. Therefore, excited 4HOBP is quickly deprotonated to 4OBP--S0 in ∼neutral solution, with a considerable loss of the fluorescence properties. Higher fluorescence intensity can be observed under acidic conditions, where excited-state deprotonation is less effective, and in basic solution where the dissociated 4OBP--S0 form prevails as the ground state. The excited states of 4OBP- are formed directly upon radiation absorption, and being weak bases they do not undergo important acid-base equilibria. Therefore, they can undergo radiational deactivation to produce significant fluorescence emission.

Combustive, Postcombustive, and Tropospheric Butadiyne Oxidation by O2, Following Initial HO Attack. Theoretical Study.

Butadiyne (diacetylene, HC(4)H) is produced during combustions, and has been quantified in different flames as well as a biomass burning emission. Its reaction with the hydroxyl radical, HO((2)Π(3/2)), under combustion conditions, was investigated in a thorough RRKM study by J. P. Senosiain, S. J. Klippenstein, and J. A.Miller (Proc. Combust. Inst. 2007, 31, 185−192). The present densityfunctional theory (DFT) study focuses on the mechanism of further oxidation by O(2)(3Σ(g)(−)). The DFT(M06-2X)/cc-pVTZ reaction energy hypersurface for the system C(4)H(2)/HO•/O(2) is studied to define a variety of reaction pathways, and the relevant thermochemistry for temperatures ranging from 200 to 2500 K is assessed, thus encompassing combustive, postcombustive, and tropospheric conditions.Energies are then recomputed at the coupled cluster level[CCSD(T)/cc-pVTZ], and combined with the DFT thermochemistry.Finally, the role of the different reaction channels is assessed by RRKM-ME simulations in the same temperature range for P = 1 atm,to comprise the situation of emission in the troposphere and those pertaining to different flames. This shows that, when considering HO addition to the triple bond, dioxygen takes part in C(4)H(2) oxidation with higher efficiency at lower temperatures, whereas, as T rises, the O(2) adducts are inclined to redissociate: for instance, a 50% redissociation is estimated at T = 1800 K. For 200 < T < 1100 K, two polycarbonyl products (CHO.CO.CCH and CHO.CO.CHCO) and two fragmentation products (HCOOH plus OC(•)−CCH) are the main species predicted as products from the addition channel (fragmentation is entropy-favored by higher T values). However, at higher temperatures, aninitial H abstraction by HO can give the but adiynyl radical (HC(4)(•)) as the starting point for subsequent dioxygen intervention.Then, new pathways opened by O(2) addition become accessible and bring about fragmentations mainly to HC(3)(•) + CO(2) and also to HC(3)(•)O + CO.

Tuning of the Electronic Properties of Armchair Graphene Nanoribbons through Functionalization: Theoretical Study of (1)Δg O2 Border Addition.

We report the results of a DFT study of the border oxidation by (1) Δg O2 of molecular models of armchair graphene nanoribbons (a-GNRs). The aim of this work is to propose a new method, as an alternative or complementary method to the tuning of the size, to modify the electronic properties of a-GNRs. Here, we investigate modification of the HOMO and LUMO energies, which are some of the most important parameters to be controlled in the design of organic electronic devices. We study the oxidation reaction mechanism of medium-size polycyclic aromatic hydrocarbons, mimicking the stiffness and reactivity of a-GNRs. Thermodynamics and kinetics indicate that the reaction should bring about a decoration of the borders with vicinal dialdehyde groups. We also study the effect of this oxidation on the HOMO and LUMO energies of two series of molecular models of a-GNRs with increasing lengths. The results suggest that the oxidized a-GNRs should present LUMO energies lowered by 0.3-0.5 eV with respect to the original material, whereas the HOMO energies are barely lowered.

o-Benzyne fragmentation and isomerization pathways: a CASPT2 study.

The mechanisms of the fragmentation and isomerization pathways of o-benzyne were studied at the multi-configurational second-order perturbative level [CAS(12,12)-PT2]. The direct fragmentation of o-benzyne to C2H2 + C4H2 follows two mechanisms: a concerted mechanism and a stepwise mechanism. Although the concerted mechanism is characterized by a single closed-shell transition structure, the stepwise pathway is more complex and structures with a strong diradical character are seen. A third diradicaloid fragmentation pathway of o-benzyne yields C6H2 as the final product. As an alternative to fragmentation, o-benzyne can also undergo rearrangement to its meta and para isomers and to the open chain cis and trans isomers of hexa-3-en-1,6-diyne (HED). These easily fragment to C2H2 + C4H2 or C6H2. Kinetic modelling at several different temperatures between 800 and 3000 K predicted that the thermal decomposition of o-benzyne should yield C2H2, C4H2 and C6H2 as the main products. Small amounts of the HED isomers accumulated at temperatures <1200 K, but they rapidly decompose at higher temperatures. Between 1000 and 1400 K, C2H2 + C4H2 are formed exclusively from the decomposition of trans-HED. At temperatures >1400 K, C2H2 + C4H2 also form from the direct fragmentation of o-benzyne. The formation of C2H2 + C4H2 prevails up to 1600 K but above this temperature the formation of C6H2 prevails. At temperatures >2400 K, the direct fragmentation of o-benzyne again leads to the formation of C2H2 + C4H2. The formation of hydrogen atoms is also explained by our proposed mechanisms.

Tailoring fluorescent strigolactones for in vivo investigations: a computational and experimental study.

Strigolactones (SLs) are a new class of plant hormones whose role has been recently defined in shoot branching, root development and architecture, and nodulation. They are also active in the rhizosphere as signalling molecules in the communication between plants, AMF (arbuscular mycorrhizal fungi) and parasitic weeds. In spite of the crucial and multifaceted biological role of SLs, the current knowledge on the SL biosynthetic pathway and the perception/transduction mechanism is still incomplete. Both genetic and molecular approaches are required to understand the molecular mechanism by which SLs regulate plant development. Our contribution to this topic is the design and synthesis of fluorescent labelled SL analogues to be used as probes for the detection in vivo of the receptor(s). Knowledge of the putative receptor structure will boost the research on analogues of the natural substrates as required for agricultural applications.

First ring formation by radical addition of propargyl to but-1-ene-3-yne in combustion. Theoretical study of the C7H7 radical system.

Combustive formation of a first carbon ring is an important step in the growth of polycyclic aromatic hydrocarbons (PAHs) and soot platelets. Propargyl radical addition to but-1-ene-3-yne (vinylacetylene) can start this process, possibly forming 5-, 6-, and 7-membered rings. A variety of partially intertwined reaction pathways results from density functional theory (DFT), which indicates three C7H7 radicals, benzyl, tropyl, and vinylcyclopentadienyl, as particularly stable. DFT energetics forms a basis for a subsequent Rice-Ramsperger-Kassel-Marcus (RRKM) study at different combustion pressures and temperatures (P = 30-0.01 atm; T = 1200-2400 K). RRKM indicates open-chain structures and 5-rings as the most important products. Open-chain structures, whose main contributors are the initial adducts, are favored by lower T and higher P, while 5-rings are favored by higher T and lower P. The main feature is that the declining yield in open-chain structures with rising T almost mirrors, at all pressures, the growth with T exhibited by 5-rings (main contributor: fulvenallene). Thus, the two yield lines for open chains and 5-rings cross at some T, and their crossing moves toward lower T values as lower P values are considered. Because the T dependence of the yields (slope of the lines) is more pronounced in the T range close to the line crossing, it also becomes less pronounced at the lowest P values considered because the crossing region falls at very low T values. Another constant trait is that 6-rings (mainly benzyl radical) are the third contributor, though they are present at most with a modest maximum yield of 2.4-2.7% in a T range which moves toward lower T as P is reduced.

Memory effects in carbocation rearrangements: structural and dynamic study of the norborn-2-en-7-ylmethyl-X solvolysis case.

The solvolysis of two diastereomers may give the same two products, but in different ratios, notwithstanding the fact that the two reaction pathways share an apparently identical intermediate carbocation. This has been dubbed the "memory effect", since the initial carbocation seems to "remember" its origin when undergoing further evolutions through multistep rearrangements. This puzzling result was studied theoretically for the case of the solvolysis of norborn-2-en-7-ylmethyl-X systems by defining the reaction potential energy surface (PES) and then carrying out a dynamical study. The PES shows that upon X(-) loss, multiphase rearrangements concertedly yield the two stablest carbocations, G and L. These carbocations are connected by a transition structure. The carbocation intermediates proposed in the literature do not correspond to any stationary point. The preference for the rearrangement to G or L (the memory effect) is determined by structural and stereoelectronic effects: the competitive interaction between an empty p orbital with a σ orbital or a p/π orbital is guided by geometrical aspects present in the starting carbocations. The dynamical study shows that (1) G and L do not interconvert and (2) the evolving system can switch from one pathway to the other to different extents, thus determining a more or less pronounced memory loss (the leakage).

Photochemical transformation of ibuprofen into harmful 4-isobutylacetophenone: pathways, kinetics, and significance for surface waters.

The harmful compound 4-isobutylacetophenone (IBAP) can be formed photochemically from the anti-inflammatory drug ibuprofen (IBP), upon direct photolysis (yield 25 ± 7%, µ ± σ), reaction with ·OH (yield 2.3 ± 0.1%) and reaction with triplet states of chromophoric dissolved organic matter, (3)CDOM* (yield 31 ± 4%). In the latter case, anthraquinone-2-sulphonate was used as CDOM proxy. The three processes would account for most of the photochemical transformation of IBP and IBAP in surface waters. IBAP formation from IBP involves the propanoic acid chain, which is more reactive than the aromatic ring as shown by quantum mechanical calculations. IBAP is expected to undergo slightly faster photochemical transformation than IBP in surface waters, with a modelled pseudo-first order rate constant that is higher by 1.5-1.9 times compared to IBP. Due to fairly high formation yields and depending on IBP emission scenarios, photochemical modelling suggests that IBAP could reach concentration values up to ~15% of IBP in surface waters, thus being a potentially important transformation intermediate. This issue prompts for the need of field studies that provide information on IBAP environmental occurrence, which is virtually unknown at the present moment.

o-Benzenedisulfonimide and its chiral derivative as Brønsted acids catalysts for one-pot three-component Strecker reaction. Synthetic and mechanistic aspects.

o-Benzenedisulfonimide (OBS) has efficiently catalysed the one-pot three-component reaction of ketones and aromatic amines with trimethylsilyl cyanide (TMSCN) giving the corresponding α-amino nitriles in excellent yields (23 examples; average yield 85%). Reaction conditions were very simple, green and efficient. Theoretical calculations have allowed us to explain the mechanism of this reaction which has been found to take place in two phases; the first consists of the nucleophilic addition of the aniline to the ketone and the subsequent dehydration to an imine; the second one consists of the formal addition of cyanide anion to the protonated imine. OBS acts in all steps of this mechanism. Without an acid catalyst, the reaction mechanism is more simple but barriers are sensibly higher. A chiral derivative of OBS was also used and gave fairly good results.

Border reactivity of polycyclic aromatic hydrocarbons and soot platelets toward ozone. A theoretical study.

PAH-based models, with an even or odd number of unsaturated carbon atoms and π electrons (even and odd PAHs for short), are selected to investigate, by molecular and periodic methods, their electron distribution and border reactivity toward ozone, and also to represent local features and edge reactivity of even or odd soot platelets. These results will contrast those previously collected for the internal positions of similar even (J. Phys. Chem. A 2005, 109, 10929.) or odd systems (J. Phys. Chem. A 2008, 112, 973.). Topologically different peripheral positions, representative of armchair and zigzag borders, exhibit different reactivity right from the beginning. Ozone attacks start off either to give primary ozonides by concerted addition or, nonconcertedly, to first produce trioxyl intermediates. Then, a variety of pathways are described, whose viability depends on both model and position. They can open the way to the possible formation of epoxide, aldehyde, and phenol groups (all entailing O(2) production) or ether (+CO(2)), lactone (+H(2)CO), and ketone functionalities. To sum up, functionalization, regardless of how achieved, can give a number of groups, most of which actually observed in PAH ozonization experimental studies. This picture can be matched up to the results on internal sites of our preceding papers, for which epoxidation was the only outcome. Most interestingly, formation of a ketone group may turn an even system into an odd one (and conversely) while involving production of HOO(•).

Polycyclic aromatic hydrocarbon formation mechanism in the "particle phase". A theoretical study.

The synthesis of polycyclic aromatic hydrocarbons (PAHs) and the formation of soot platelets occur both during combustion at relatively low [O(2)], or under pyrolysis conditions. When the PAH size grows beyond the number of three-four condensed cycles, the partitioning of PAHs between the gas and particle phases favours the latter (i.e. adsorption). This study aims to assess which role the soot particle plays during PAH synthesis, in particular if catalytic or template effects of some sort can be exerted by the soot platelet on the adsorbed growing PAH-like radical. Our theoretical calculations indicate that chain elongation by ethyne addition cannot compete with cyclization when both can take place in the growing PAH-like radical, already in the gas phase. When it is adsorbed, cyclization is found to become easier than in the gas phase (more so, in terms of Gibbs free energy barriers, at higher temperatures), hinting at some sort of template effect, while chain elongation by ethyne addition becomes somewhat more difficult. The underlying soot platelet can assist (at lower temperatures) the formation of a larger aromatic hydrocarbon, by a final hydrogen abstraction from that endocyclic saturated carbon the newly formed cycle still bears. As an alternative (at higher temperature), a spontaneous hydrogen atom loss can take place. Finally, at rather low temperatures, the addition of the growing radical to the underlying soot platelet might occur and cause some reticulation, form more disordered structures, i.e. soot precursors instead of PAHs.

The mechanism of the Stevens and Sommelet-Hauser rearrangements. A theoretical study.

The [1,2] and [2,3] migration steps in the Stevens and Sommelet-Hauser rearrangements which occur in the ylides of quaternary ammonium salts have been studied at M05-2x levels. The Stevens migration has been found to take place through a diradical pathway in several cases (tetramethylammonium, benzyltrimethylammonium, benzylphenacyldimethylammonium ylides). By contrast, in the phenyltrimethylammonium ylide this reaction takes place through a concerted process. The Sommelet-Hauser rearrangement takes place through a concerted transition structure. The most important factor determining the extent of competition with the Stevens rearrangement is the difference in the reaction energies as the formation of the Sommelet-Hauser intermediate is significantly less endoergic.