Nucleophilic Substitution Reaction of p-Dinitrobenzene by a Carbanion: Evidence for Electron Transfer Mechanism

ＩｎｔｒｏｄｕｃｔｉｏｎＳｉｎｇｌｅｅｌｅｃｔｒｏｎｔｒａｎｓｆｅｒｉｎａｒｏｍａｔｉｃｎｕｃｌｅｏｐｈｉｌｉｃｓｕｂ ｓｔｉｔｕｔｉｏｎｈａｓａｔｔｒａｃｔｅｄｍｕｃｈａｔｔｅｎｔｉｏｎｉｎｒｅｃｅｎｔｙｅａｒｓ .Ｉｎａｄｄｉｔｉｏｎｔｏｔｈｅｗｅｌｌ ｋｎｏｗｎＳＲＮ1ｍｅｃｈａｎｉｓｍｒｅｐｏｒｔｅｄｂｙＢｕｎｎｅｔｔ,1ｍａｎｙｏｔｈｅｒａｃｔｉｖａｔｅｄａｒｏｍａｔｉｃｓｙｓｔｅｍｓ ,ｉ .ｅ .,ｎｉｔｒｏａｒｙｌｈａｌｉｄｅｓ ,ｄｉｎｉｔｒｏｂｅｎｚｅｎｅｓ ,ｅｔｃ .,ｈａｖｅｂｅｅｎｒｅ ｐ…     

Conjugate Addition of a Silyl Ketene Acetal to α,β‐Unsaturated Lactones

Abstract

Conjugate addition of a silyl ketene acetal [Me₂C?C (OMe)OSiMe₃] to α,β‐unsaturated lactones (namely, 5,6‐dihydro‐2H‐pyran‐2‐one, 2(5H)‐furanone as Michael acceptor) occurs efficiently at room temperature in the presence of a nucleophilic catalyst, tetra‐n‐butyl ammonium bibenzoate (TBABB), in THF as well as Lewis acid catalysts such as Yb(OTf)₃ and I₂ in CH₂Cl₂, giving the corresponding 1,4‐adducts in excellent yields.     

Addition of a Silyl Ketene Acetal to α,β-Unsaturated Cyclic Anhydrides

Addition of [1-methoxy-2 methyl-1-propenyl)-oxy] trimethylsilane (MTS) to unsymmetrical α,β-unsaturated cyclic anhydrides (namely, itaconic anhydride and citraconic anhydride) as well as symmetrical anhydrides (namely, maleic anhydride and 2,3-dimethylmaleic anhydride) was investigated. Itaconic anhydride isomerizes to citraconic anhydride in the presence of MTS. In the presence of Lewis acid catalysts (Yb(OTf)₃/CH₂Cl₂), MTS adds to itaconic anhydride at room temperature in a 1,4-fashion. 1,2-Addition is the preferred pathway with both 2,3-dimethyl maleic anhydride and citraconic anhydride.     

Novel Photoinduced Electron Transfer Reaction of N-methylphenothiazine in Carbon Tetrachloride

PhenothiazinederivativeshaveattractedmuchinterestforalongtimeduetotheirdiversechemicalandbioIogicalproperties,aswellasmedicalaPplicationsl.Theradicalcationofphenothiazinesisbelievedtobeinvolvedinthebiotransformationofphenothiazinedrugs2andnumerousstudieshavethusfocusedonthegenerationandreactionsofphenothiazineradicalcations3-6.WereporthereinanovelphotochemicalreactionofN-methylphenothiazineincarbontetrachloridewhichcoupIestwoparentmoleculeswitheliminationofonemethylgroup(Schemel).Resultsandd…     

Regioselective Addition of Silyl Enolates to α, β-Unsaturated Aldehyde and its Acetal Catalyzed by MgI_2 Etherate

In our previous letter1, we have reported the unique catalytic reactivity of MgI2 etherate 1 in the chemoselective Mukaiyama-type aldol reactions of aryl or vinyl aldehyde and aldehyde acetals with silyl enolates. Aryl or alkyl a, b-unsaturated aldehydes (and their acetals) are particularly reactive in this catalytic addition reaction due to possibly the effective activation of the electron-rich carbonyl by highly oxyphilic Lewis acidic species, i.e. IMg+, in non-coordinative media (i.e. CH…     

Regioselective Addition of Silyl Enolates to α,β－Unsaturated Aldehyde and its Acetal Catalyzed by MgI2 Etherate

Regioselective addition reactions of silyl enolates to α,β-unsaturated aldehyde and its acetal catalyzed by MgI2 etherate give aldol adducts (1, 2-addition) preferentially over Michael adducts (1, 4-addition). This unique regioselectivity is distinctly different with other Lewis acidic promoters and may be attributed to the high oxyphilicity of IMg^ .     

Photochemical Reaction Mechanism of Intramolecular H Transfer Reaction of H2C3O+⋅ Radical Cation

The photochemical reaction mechanism underlying the intramolecular H-transfer of the H₂C₃O⁺⋅ radical cation to the H₂CCCO⁺⋅ methylene ketene cation was elucidated using time-dependent density functional theory and high-level ab initio methods. Once the D₁ state of H₂C₃O⁺⋅ is populated, the reaction proceeds to form an intermediate (IM) in the D₁ state (IM4_D1). The molecular structure of the conical intersection (CI) was optimized using a multiconfigurational ab initio method. The CI is readily accessible because it lies slightly above the IM4_D1 in energy. In addition, the gradient difference vector of the CI is almost parallel to the intramolecular H-transfer reaction coordinate. Once the vibration mode of IM4_D1 which is parallel to the reaction coordinate is populated, the degeneracy of the CI is readily lifted and H₂CCCO⁺⋅ was formed via a relaxation pathway in the D₀ state. Our calculated results clearly describe the photochemical intramolecular H transfer reaction reported in a recent study.     

Theoretical Study on the Reaction Mechanism of Ketene CH2CO with Isocyanate NCO Radical

The bimolecular single collision reaction potential energy surface of an isocyanate NCO radical with a ketene CH2CO molecule was investigated by means of B3LYP and QCISD（T） methods. The computed results indicate that two possible reaction channels exist on the surface. One is an addition-elimination reaction process, in which the CH2CO molecule is attacked by the nitrogen atom at its methylene carbon atom to lead to the formation of the intermediate OCNCH2CO followed by a C-C rupture channel to the products CH2NCO＋CO. The other is a direct hydrogen abstraction channel from CHzCO by the NCO radical to afford the products HCCO＋HNCO. Because of a higher barrier in the hydrogen abstraction reaction than in the addition-elimination reaction, the direct hydrogen abstraction pathway can only be considered as a secondary reaction channel in the reaction kinetics of NCO＋ CH2CO. The predicted results are in good agreement with previous experimental and theoretical investigations.     

Quantum Chemical Study on a New Mechanism of One-carbon Unit Transfer Reaction： The Water-assisted Mechanism

It is a theoretical study on the water-assisted mechanism of one-carbon unit transfer reaction, in which the energy barrier for each transition state lowered by about 80-100 kJ/mol when compared with the one in no-water-involved mechanism. The water-assisted path 4 is the favorite reaction way. Our results well explained the presumption from experiments.     

Consecutive Photoinduced Electron Transfer (conPET): The Mechanism of the Photocatalyst Rhodamine 6G

The dye rhodamine 6G can act as a photocatalyst through photoinduced electron transfer. After electronic excitation with green light, rhodamine 6G takes an electron from an electron donor, such as N,N-diisopropylethylamine, and forms the rhodamine 6G radical. This radical has a reduction potential of around −0.90 V and can split phenyl iodide into iodine anions and phenyl radicals. Recently, it has been reported that photoexcitation of the radical at 420 nm splits aryl bromides into bromide anions and aryl radicals. This requires an increase in reduction potential, hence the electronically excited rhodamine 6G radical was proposed as the reducing agent. Here, we present a study of the mechanism of the formation and photoreactions of the rhodamine 6G radical by transient absorption spectroscopy in the time range from femtoseconds to minutes in combination with quantum chemical calculations. We conclude that one photon of 540 nm light produces two rhodamine 6G radicals. The lifetime of the photoexcited radicals of around 350 fs is too short to allow diffusion-controlled interaction with a substrate. A fraction of the excited radicals ionize spontaneously, presumably producing solvated electrons. This decay produces hot rhodamine 6G and hot rhodamine 6G radicals, which cool with a time constant of around 10 ps. In the absence of a substrate, the ejected electrons recombine with rhodamine 6G and recover the radical on a timescale of nanoseconds. Photocatalytic reactions occur only upon excitation of the rhodamine 6G radical, and due to its short excited-state lifetime, the electron transfer to the substrate probably takes place through the generation of solvated electrons as an additional step in the proposed photochemical mechanism.     

Theoretical Study on the Kinetics of Electron Transfer for Bond—breaking Reaction

ＩｎｔｒｏｄｕｃｔｉｏｎＦｒｅｅｒａｄｉｃａｌｆｏｒｍａｔｉｏｎｆｒｏｍｈａｌｏｇｅｎａｔｅｄｈｙｄｒｏｃａｒｂｏｎｓｈａｓｒｅｃｅｉｖｅｄｃｏｎｓｉｄｅｒａｂｌｅａｔｔｅｎｔｉｏｎｂｅｃａｕｓｅｏｆｉｔｓｓｃｉｅｎｔｉｆ ｉｃａｎｄｅｎｖｉｒｏｎｍｅｎｔａｌｒｅｌｅｖａｎｃｅ .1 6 Ｔｈｉｓｒｅａｃｔｉｏｎｓｅｅｍｓｔｏｐｌａｙａｎｉｍｐｏｒｔａｎｔｒｏｌｅｉｎｖａｒｉｏｕｓｐｒｏｃｅｓｓｅｓ .Ｂｏｎｄ ｂｒｅａｋ ｉｎｇｒｅａｃｔｉｏｎｉｓａｐｏｗｅｒｆｕｌｓｙｎｔｈｅｔｉｃｔｏｏｌｔｏｐｒｏｖ…     

Effect of Silyl Moiety on the Reaction of O,O''''-Phenylenephosphoryl Chloride with N-Silylvaline Silyl Ester

Itwasproposedthatthemixedcarboxylic-phosphoricanhydridelikepentacovalentphosphorousintermediatesactedasthekeystepofthecomplicatedselfcatalysedreactionsofNphospho-Q-aminoacids'.Inordertorationalisethemechanism,modelpentacoordinatedcompoundsweresynthesisedbythereactionofo.O--phenylenephosphorylchloridelwithNtrdriethylsilyl-a-aminoacidtrdriethylsily1esters.andthekineticdynamicstUdyofthisreactiongaveadirectevidenceoftheside-chainparticipationoftheaminoacidsmoieties'.Inthispaperwewil1demonstratet…     

Proton or Carbene Transfer? On the Dark and Light Reaction of Diazoalkanes with Alcohols

The formal alkylation reaction of OH groups with diazoalkanes under catalyst-free reaction conditions finds broad application in organic synthesis. However, even today, this reaction is mainly limited to the use of diazomethane as reaction partner. In this combined experimental and theoretical study, we aim at a fundamental understanding of the reaction of diazoalkanes with alcohols to make this transformation amenable to a generalized approach towards formal alkylation reactions of alcohols with diazoalkanes. Experimental and theoretical studies suggest a direct proton transfer only in exceptional cases. In a more general setting, such O−H functionalization proceed both under dark and photochemical conditions via a key hydrogen-bonded singlet carbene intermediate that undergoes a protonation–addition mechanism. We conclude with applications of this approach in O−H functionalization reactions of alcohols, including simple fluorinated, halogenated and aliphatic alcohols and showcase functional-group tolerance of this method in the reaction of biologically active and pharmaceutically relevant alcohols.     

The Electron Transfer Reaction between p-Nitrobenzoates and β-N，N-Dimethylaminonaphthalene

A few of p-nitrobenzoates were synthesized,and the electron transfer of them with β-N,N-dimethylaminonaphthalene (DMAN) in methanol solution was studied.Steady-state fluorescence results showed the cyclodextrin moicty in p-nitrobenzoyl-β-cyclodextrin would block the electron transfer pathway from DMAN compared with other electron acceptors,thus ,reduced the electron transfer efficiency.     

Nonequilibrium Solvent Free Energy Curve from Molecular Theory in Electron Transfer Reaction

l.IntroductionEleCtrontransfer(ET)reactionisamongthemostfundaInentalofcheIIilstryandbiochendsny.Thetwrtanroleofevaluationofthes0lventfreeenergyandthercorganhaionenergyaninETprocesshasalwaysbeenreeogfordbyanextensiveliteratureindilsfield[1-2].HeneehowtochooseasuitablesolventreactioncoordinaeandconsequentlyconstructtheassociatedfreeenergyfimtionbecomesthCpriInnysteP,andalsotheaPplicabilityoftheenergygaPlaw.Manyrecentstudiesarefocusedonthesolventpolarizaionandsolventdyndcalbehaviorandmpmeeh…     

Modification of Nano-alumina Surface by Michael Addition Reaction

With recent interest in polymer-based nanocomposites, nano-alumina has receivedconsiderable attention because of their high hardness, high strength and good wearresistance. Improvements in mechanical, tribological, conductive and barrier propertiesof some…     

Electron Transfer Reaction Between Desoxyadenosine and Triplet 2-Methyl-1,4-naphthaquinone:A Laser Photolysis Study

Introduction ElectrontransferoxidationofDNAbytripletartifi cialphotonucleaserevealsabrightprospectofitsappli cationinbiologyandmedicine.Bothmolecularorbital calculationandlaserexperimentshaveindicatedthat thehomoguaninesequenceshouldbethefinallocaliza tio…     

What Hinders Electron Transfer Dissociation (ETD) of DNA Cations?

Radical activation methods, such as electron transfer dissociation (ETD), produce structural information complementary to collision-induced dissociation. Herein, electron transfer dissociation of 3-fold protonated DNA hexamers was studied to gain insight into the fragmentation mechanism. The fragmentation patterns of a large set of DNA hexamers confirm cytosine as the primary target of electron transfer. The reported data reveal backbone cleavage by internal electron transfer from the nucleobase to the phosphate linker leading either to a?/w or d/z? ion pairs. This reaction pathway contrasts with previous findings on the dissociation processes after electron capture by DNA cations, suggesting multiple, parallel dissociation channels. However, all these channels merely result in partial fragmentation of the precursor ion because the charge-reduced DNA radical cations are quite stable. Two hypotheses are put forward to explain the low dissociation yield of DNA radical cations: it is either attributed to non-covalent interactions between complementary fragments or to the stabilization of the unpaired electron in stacked nucleobases. MS³ experiments suggest that the charge-reduced species is the intact oligonucleotide. Moreover, introducing abasic sites significantly increases the dissociation yield of DNA cations. Consequently, the stabilization of the unpaired electron by π–π-stacking provides an appropriate rationale for the high intensity of DNA radical cations after electron transfer.

Open image in new window

Graphical Abstract

     

Mechanism of HCS + O2 reaction: hydrogen- or oxygen-transfer?

In spite of the potential importance of the HCS radical in both combustion and interstellar processes, its chemical reactivity has not been tackled previously. In the present paper, the oxidation reaction of the HCS radical is theoretically investigated for the first time at the CCSD(T)/6-311++G(3df,2p)//BH&HLYP/6-311++G(d,p)+ZPVE and Gaussian-3//B3LYP/6-31G(d) levels. It is shown that the most feasible pathway is the O2 addition to the HCS radical forming the intermediate SC(H)OO which can undergo a subsequent O-extrusion leading to SC(H)O + 3O. This features an indirect O-transfer mechanism with the overall barrier of 4.4 and 3.5 kcal mol(-1), respectively, at the two levels. However, formation of the H-transfer product CS + HO2 is kinetically much less feasible, i.e., the direct mechanism has barriers of 14.3 and 8.7 kcal mol(-1), whereas the indirect mechanism has barriers of 12.6 and 10.7 kcal mol(-1), respectively. This result is in sharp contrast to the analogous HCO + O2 reaction, where the direct (with a barrier of 2.98 kcal mol(-1)) and indirect (2.26 kcal mol(-1)) H-transfer processes are highly competitive over the indirect O-transfer process (the least endothermicity is 19.9 kcal mol(-1)). The possible explanations and implications of the present results are provided.