Rate constants for the gas‐phase reactions of a series of C3?C6 aldehydes with OH and NO3 radicals

By using relative rate methods, rate constants for the gas‐phase reactions of OH and NO₃ radicals with propanal, butanal, pentanal, and hexanal have been measured at 296 ± 2 K and atmospheric pressure of air. By using methyl vinyl ketone as the reference compound, the rate constants obtained for the OH radical reactions (in units of 10⁻¹² cm³ molecule⁻¹ s⁻¹) were propanal, 20.2 ± 1.4; butanal, 24.7 ± 1.5; pentanal, 29.9 ± 1.9; and hexanal, 31.7 ± 1.5. By using methacrolein and 1‐butene as the reference compounds, the rate constants obtained for the NO₃ radical reactions (in units of 10⁻¹⁵ cm³ molecule⁻¹ s⁻¹) were propanal, 7.1 ± 0.4; butanal, 11.2 ± 1.5; pentanal, 14.1 ± 1.6; and hexanal, 14.9 ± 1.3. The dominant tropospheric loss process for the aldehydes studied here is calculated to be by reaction with the OH radical, with calculated lifetimes of a few hours during daytime. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 79–84, 2000     

Can quasiclassical trajectory calculations reproduce the extreme kinetic isotope effect observed in the muonic isotopologues of the H + H2 reaction?

Rate coefficients for the mass extreme isotopologues of the H + H(2) reaction, namely, Mu + H(2), where Mu is muonium, and Heμ + H(2), where Heμ is a He atom in which one of the electrons has been replaced by a negative muon, have been calculated in the 200-1000 K temperature range by means of accurate quantum mechanical (QM) and quasiclassical trajectory (QCT) calculations and compared with the experimental and theoretical results recently reported by Fleming et al. [Science 331, 448 (2011)]. The QCT calculations can reproduce the experimental and QM rate coefficients and kinetic isotope effect (KIE), k(Mu)(T)/k(Heμ)(T), if the Gaussian binning procedure (QCT-GB)--weighting the trajectories according to their proximity to the right quantal vibrational action--is applied. The analysis of the results shows that the large zero point energy of the MuH product is the key factor for the large KIE observed.     

Quantum instanton calculation of rate constants for the C2H6 + H → C2H5 + H2 reaction: anharmonicity and kinetic isotope effects

Thermal rate constants and kinetic isotope effects for the title reaction are calculated by using the quantum instanton approximation within the full dimensional Cartesian coordinates. The obtained results are in good agreement with experimental measurements at high temperatures. The detailed investigation reveals that the anharmonicity of the hindered internal rotation motion does not influence the rate too much compared to its harmonic oscillator approximation. However, the motion of the nonreactive methyl group in C(2)H(6) significantly enhances the rates compared to its rigid case, which makes conventional reduced-dimensionality calculations a challenge. In addition, the temperature dependence of kinetic isotope effects is also revealed.     

Palladium‐Catalyzed Direct Dialkenylation of Cage B?H Bonds in o‐Carboranes through Cross‐Coupling Reactions

Palladium‐catalyzed direct dialkenylation of cage B(4,5) H bonds in o‐carboranes has been achieved with the help of a carboxylic acid directing group, leading to the preparation of a series of 4,5‐[trans‐(ArCHCH)]₂‐ocarboranes in high yields with excellent regioselectivity. The traceless directing group, eliminated during the course of the reaction, is responsible for controlling regioselectivity and dialkenylation. A possible catalytic cycle is proposed, involving a tandem sequence of Pd^II‐initiated cage B H activation, alkene insertion, β‐H elimination, reductive elimination, and decarboxylation.     

Internal energy disposal in the chemiluminescent reaction CD + NO → ND(A) + CO and the kinetic isotope effect

The vibrational and rotational energy disposal for ND(A) from the CD + NO reaction was measured in a flowing afterglow. The initial vibrational and rotational distributions of ND(A) were obtained from a spectral simulation. The initial vibrational distribution was (0.51 ± 0.05)_{ν′ = 0}: (0.26 ± 0.05)_{ν′ = 1}: (0.16 ± 0.05)_{ν′ = 2}: (0.07 ± 0.05)_{ν′ = 3}. The rotational temperatures in ν′ = 0, 1, 2 and 3 levels were 4500 ± 500, 4000 ± 500, 4000 ± 500 and 4000 ± 500 K, respectively. The fractions of the available energy deposited into the vibration, 〈fv〉 and rotation, 〈f_R〉, were 0.21 and 0.36, respectively. The results for ND(A) were compared with those for NH(A) from the CH + NO reaction reported previously and the reaction dynamics was discussed on the basis of the observed isotope effect on the energy state distributions. The kinetic isotope effect k_H/k_D in the CH, CD + NO reactions was measured to be 1.84 ± 0.23. The experimental result was compared with a theoretical calculation using transition-state theory.     

Catalytic C?C,C?N,and C?O Ullmann‐Type Coupling Reactions

Copper‐catalyzed Ullmann condensations are key reactions for the formation of carbon–heteroatom and carbon–carbon bonds in organic synthesis. These reactions can lead to structural moieties that are prevalent in building blocks of active molecules in the life sciences and in many material precursors. An increasing number of publications have appeared concerning Ullmann‐type intermolecular reactions for the coupling of aryl and vinyl halides with N, O, and C nucleophiles, and this Minireview highlights recent and major developments in this topic since 2004.     

Iron‐Promoted C?C Bond Formation in the Gas Phase

An unusual iron transfer and carbon–carbon coupling take place in gas‐phase ionized mixtures containing ferrocene and dichloromethane. Ferrous chloride and the protonated benzenium ion are eventually formed by a thermal and efficient reaction, through stable intermediates that undergo a remarkable reorganization. The mechanism of the concerted iron extrusion, carbon–chlorine bond activation and carbon–carbon bond formation is elucidated by electronic structure calculations that show the crucial role of iron.     

Synthesis of Di‐, Tri‐, and Tetrasubstituted Oxetanes by Rhodium‐Catalyzed O?H Insertion and C?C Bond‐Forming Cyclization

Oxetanes offer exciting potential as structural motifs and intermediates in drug discovery and materials science. Here an efficient strategy for the synthesis of oxetane rings incorporating pendant functional groups is described. A wide variety of oxetane 2,2‐dicarboxylates were accessed in high yields, including functionalized 3‐/4‐aryl‐ and alkyl‐substituted oxetanes and fused oxetane bicycles. Enantioenriched alcohols provided enantioenriched oxetanes with complete retention of configuration. The oxetane products were further derivatized, while the ring was maintained intact, thus highlighting their potential as building blocks for medicinal chemistry.     

Nickel‐Catalyzed Enantioselective C?C Bond Formation through C?O Cleavage in Aryl Esters

We report the first enantioselective C C bond formation through C O bond cleavage using aryl ester counterparts. This method is characterized by its wide substrate scope and results in the formation of quaternary stereogenic centers with high yields and asymmetric induction.     

Redox‐Neutral Rhodium‐Catalyzed C?H Functionalization of Arylamine N‐Oxides with Diazo Compounds: Primary C(sp3)?H/C(sp2)?H Activation and Oxygen‐Atom Transfer

An unprecedented rhodium(III)‐catalyzed regioselective redox‐neutral annulation reaction of 1‐naphthylamine N‐oxides with diazo compounds was developed to afford various biologically important 1H‐benzo[g]indolines. This coupling reaction proceeds under mild reaction conditions and does not require external oxidants. The only by‐products are dinitrogen and water. More significantly, this reaction represents the first example of dual functiaonalization of unactivated a primary C(sp³) H bond and C(sp²) H bond with diazocarbonyl compounds. DFT calculations revealed that an intermediate iminium is most likely involved in the catalytic cycle. Moreover, a rhodium(III)‐catalyzed coupling of readily available tertiary aniline N‐oxides with α‐diazomalonates was also developed under external oxidant‐free conditions to access various aminomandelic acid derivatives by an O‐atom‐transfer reaction.     

Transition‐metal‐catalyzed aminations and aziridinations of C?H and CC bonds with iminoiodinanes

Catalytic insertion or addition of a metal‐imido/nitrene species, generated from reaction of a transition‐metal catalyst with iminoiodanes, to C? H and C?C bonds offers a convenient and atom economical method for the synthesis of nitrogen‐containing compounds. Following this groundbreaking discovery during the second half of the last century, the field has received an immense amount of attention with a myriad of impressive metal‐mediated methods for the synthesis of amines and aziridines having been developed. This review will cover the significant progress made in improving the efficiency, versatility and stereocontrol of this important reaction. This will include the various iminoiodanes, their in situ formation, and metal catalysts that could be employed and new ligands, both chiral and non‐chiral, which have been designed, as well as the application of this functional group transformation to natural product synthesis and the preparation of bioactive compounds of current therapeutic interest. DOI 10.1002/tcr.201100018     

Study of the pyrimidine nucleobase C5?C6 bond reactivity under thio‐michael/aldol tandem reaction conditions

Pyrimidine nucleobases can undergo a Michael/aldol tandem reaction triggered by a thiolate. In an intramolecular context, 5′‐deoxy‐2′,3′‐isopropylidene‐5′‐thiouridine affords the reminiscent Baylis‐Hillman adduct after retro‐Michael addition whereas its thymine counterpart is unreactive. In an intermolecular context, the conjugate addition‐aldol reaction occurs only if the C5? C6 double bond is activated.     

Palladium(II)‐Catalyzed C?H Activation/C?C Cross‐Coupling Reactions: Versatility and Practicality

Pick your Pd partners : A number of catalytic systems have been developed for palladium‐catalyzed C? H activation/C? C bond formation. Recent studies concerning the palladium(II)‐catalyzed coupling of C? H bonds with organometallic reagents through a Pd^II/Pd⁰ catalytic cycle are discussed (see scheme), and the versatility and practicality of this new mode of catalysis are presented. Unaddressed questions and the potential for development in the field are also addressed.

     

Thermochemistry and reaction paths in the oxidation reaction of benzoyl radical: C6H5C•(═O)

Alkyl substituted aromatics are present in fuels and in the environment because they are major intermediates in the oxidation or combustion of gasoline, jet, and other engine fuels. The major reaction pathways for oxidation of this class of molecules is through loss of a benzyl hydrogen atom on the alkyl group via abstraction reactions. One of the major intermediates in the combustion and atmospheric oxidation of the benzyl radicals is benzaldehyde, which rapidly loses the weakly bound aldehydic hydrogen to form a resonance stabilized benzoyl radical (C6H5C(?)═O). A detailed study of the thermochemistry of intermediates and the oxidation reaction paths of the benzoyl radical with dioxygen is presented in this study. Structures and enthalpies of formation for important stable species, intermediate radicals, and transition state structures resulting from the benzoyl radical +O2 association reaction are reported along with reaction paths and barriers. Enthalpies, ΔfH298(0), are calculated using ab initio (G3MP2B3) and density functional (DFT at B3LYP/6-311G(d,p)) calculations, group additivity (GA), and literature data. Bond energies on the benzoyl and benzoyl-peroxy systems are also reported and compared to hydrocarbon systems. The reaction of benzoyl with O2 has a number of low energy reaction channels that are not currently considered in either atmospheric chemistry or combustion models. The reaction paths include exothermic, chain branching reactions to a number of unsaturated oxygenated hydrocarbon intermediates along with formation of CO2. The initial reaction of the C6H5C(?)═O radical with O2 forms a chemically activated benzoyl peroxy radical with 37 kcal mol(-1) internal energy; this is significantly more energy than the 21 kcal mol(-1) involved in the benzyl or allyl + O2 systems. This deeper well results in a number of chemical activation reaction paths, leading to highly exothermic reactions to phenoxy radical + CO2 products.     

Copper‐Catalyzed Intramolecular C(sp3)?H and C(sp2)?H Amidation by Oxidative Cyclization

The first copper‐catalyzed intramolecular C(sp³) H and C(sp²) H oxidative amidation has been developed. Using a Cu(OAc)₂ catalyst and an Ag₂CO₃ oxidant in dichloroethane solvent, C(sp³) H amidation proceeded at a terminal methyl group, as well as at the internal benzylic position of an alkyl chain. This reaction has a broad substrate scope, and various β‐lactams were obtained in excellent yield, even on gram scale. Use of CuCl₂ and Ag₂CO₃ under an O₂ atmosphere in dimethyl sulfoxide, however, leads to 2‐indolinone selectively by C(sp²) H amidation. Kinetic isotope effect (KIE) studies indicated that C H bond activation is the rate‐determining step. The 5‐methoxyquinolyl directing group could be removed by oxidation.     

Does the proton-transfer reaction take place in the ground state of phenol?(H2O)4 clusters?

In recent experimental studies of infrared (IR) spectra of hydrated phenol clusters, the Mikami and Ebata group at Tohoku University attributed apparently two very different spectra to PhOH(H₂O)₄. The first spectrum has a wide transparent region between 3500 and 3700 cm^-1, which they named a window region. The second spectrum has several absorption bands in this window region. Our previous study revealed that the first spectrum was assigned to the isomers which have a single-ring structure of a hydrogen-bonding network of OH's of phenol and waters. The experimentalists suggested that the second spectrum might be identified to a proton-transferred phenol(SINGLEBOND)water cluster. In the present article, the geometrical structures of proton-transferred hydrated phenol clusters were determined with the ab initio molecular orbital method and their IR spectra were calculated. The proton-transferred phenol(SINGLEBOND)water cluster is at a stable local minimum, but the energy is much higher than that of the most stable nontransferred cluster. The calculated IR spectrum has a still wider window region and is far different from the experimental spectrum of the second type. © 1996 John Wiley & Sons, Inc.