An unexpected bispericyclic transition structure leading to 4+2 and 2+4 cycloadducts in the endo dimerization of cyclopentadiene

The stereospecific endo dimerization of cyclopentadiene takes place through an asynchronous and symmetrical bispericyclic transition structure, which shows a merging of the 4+2 and 2+4 cycloaddition paths. The shape of the transition structure testifies to the presence of attractive Salem/Houk secondary orbital interactions assisting the endo approach.     

The origin of endo stereoselectivity in the hetero-Diels-Alder reactions of aldehydes with ortho-xylylenes: CH-pi,pi-pi,and steric effects on stereoselectivity

Theoretical studies of stereoselectivity have been carried out with B3LYP and MP2 calculations. The high endo selectivity of hetero-Diels-Alder reactions of ortho-xylylenes with acetaldehydes is shown to result from attractive CH-pi interactions between alkyl groups of the aldehyde and the aromatic ring in the transition states of the reaction. For the hetero-Diels-Alder reactions of ortho-xylylenes with benzaldehyde, the stereoselectivity is shown to be mainly governed by the attractive pi-pi interactions between the phenyl rings of the benzaldehyde and the ortho-xylylene. MP2 calculations are necessary to reproduce the stabilizing dispersion interactions.     

Glycosidation of thioglycosides in the presence of bromine: mechanism, reactivity, and stereoselectivity

Elaborating on previous studies by Lemieux for highly reactive "armed" bromides, we discovered that β-bromide of the superdisarmed (2-O-benzyl-3,4,6-tri-O-benzoyl) series can be directly obtained from the thioglycoside precursor. When this bromide is glycosidated, α-glycosides form exclusively; however, the yields of such transformations may be low due to the competing anomerization into α-bromide that is totally unreactive under the established reaction conditions.     

Halobenzoyl groups in glycosylation: effect on stereoselectivity and reactivity of glycosyl donors

Described herein is the synthesis and evaluation of a series of glycosyl donors equipped with halobenzoyl substituents at O(4) and O(6) to study their properties in glycosylations. Among possible effects that may include carbonyl participation or H-bond mediated aglycone delivery, our results indicate that halobenzoyls act via a different mode.     

Quadrupole ion trap studies of the structure and reactivity of transition metal ion pair complexes

Ion pairs are common species observed in the electrospray mass spectra of transition metal coordination complexes. To understand the nature of these ion pairs, a systematic study of the gas-phase chemistry of these species using ion-molecule reactions and collision-induced dissociation (CID) was carried out. Ion pair complexes of the type MLnX+ (where M is Mn(II), Fe(II), Co(II), Ni(II), Cu(II) or Zn(II), L is 1,10-phenanthroline, 2,2'-bipyridine, ethylenediamine, diethylenetriamine or 1,4,8,11-tetraazacyclotetradecane and X is Cl-, NO3-, acetylacetonate, ClO4-, acetate or SCN-) were studied. Ion-molecule reactions can distinguish whether the counterion in an ion pair is an inner- or outer-sphere ligand and can determine the coordination mode of the counterion. In addition, CID and ion-molecule reactions reveal some interesting chemistry of these complexes and unique coordination modes for some of the anions studied here were inferred from the ion-molecule reactions. For example, the thiocyanate ion is found to coordinate in a bidentate fashion in Zn(II) and Ni(II) complexes, contrasting behavior typically observed in solution. Also, certain Co(II) and Fe(II) ion pair complexes undergo oxidation reactions in which species such as dioxygen and nitric oxide from the counterions ClO4- and NO3- are transferred to the Co(II) and Fe(II) complexes, showing the inherent affinity of these metals for these molecules. These complexes were also studied by ion-molecule reactions and CID. Dioxygen in complexes formed by CID is demonstrated to be bidentate, suggesting the formation of a peroxo ligand with concurrent oxidation of the metal.     

Proof for the existence of an early endo transition state in the Diels-Adler reactions of 2-substituted 1,3-butadienes

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1196–1197, May, 1988.     

Bond models for the photochemical reactivity of transition metal complexes

Weakening of σ bonds along the labilized axis in the lowest excited quartet state of Cr(III) complexes as estimated through σ-bond orders in a simple MO-LF model, is consistent with substitution of the stronger ligand via a mechanism initiated by a predissociative step.     

A correlation between structure and reactivity in ion clusters

Observations on metastable peaks resulting from the unimolecular decomposition of ion clusters show that intensity variations as a function of cluster size can reveal the presence of stable cluster configurations. This technique has been used to confirm that (H₂O)₂₁H⁺ and (D₂O)₂₁D⁺ are stable ion clusters, and the method also provides evidence to suggest that Ar₁₉⁺ is a particularly stable species.     

The role of Zn in enhancing the rate and stereoselectivity of the aldol reactions catalyzed by the simple prolinamide model

The aldol reaction between acetone and 4-nitrobenzaldehyde catalyzed by single l-prolinamide and its zinc complexes has been studied. An increase in the rate and the stereoselectivity of the reaction has been shown by using zinc derivatives. A mechanistic proposal, based on NMR and ESI studies, has been put forward to explain the experimental data: zinc-prolinamide complexes catalyze the reaction following the general mechanism of stereoselective enamine nucleophilic addition to the acceptor aldehyde. Zn²⁺ prevents the nonspecific base-catalyzed reaction by diminishing the basicity of the amine nitrogen of prolinamide.     

A simple and efficient approach to the synthesis of endo and exo bicyclo[6.1.0]nona-3,5-diene-9-carboxaldehyde

Monobromination of 1,5-cyclooctadiene, followed by cyclopropanation with ethyl diazoacetate, led to the formation of endo and exo ethyl 4,5-dibromobicyclo[6.1.0]nonane-9-carboxylates 3a and 3b. Bis-dehydrobromination of 3a and 3b using 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) afforded the endo and exo ethyl bicyclo[6.1.0]nona-3,5-diene-9-carboxylates 4a and 4b. Reduction of these compounds to the corresponding alcohols 5a and 5b and subsequent oxidation with pyridinium chlorochromate (PCC) resulted in the formation of the target compounds endo and exo bicyclo[6.1.0]nona-3,5-diene-9-carboxaldehydes 6a and 6b.     

Triplet reactivity and regio-/stereoselectivity in the macrocyclization of diastereomeric ketoprofen-quencher conjugates via remote hydrogen abstractions

Intramolecular excited triplet state interactions in diastereomeric compounds composed of a benzophenone chromophore (ketoprofen) and various hydrogen donor moieties (tetrahydrofuran, isopropylbenzene) have been investigated by laser flash photolysis. The rate constants for hydrogen abstraction by excited triplet benzophenone are in the order of 10(4)-10(5) s(-1), with the highest reactivity for the tetrahydrofuran residue. A remarkable diastereodifferentiation, expressed in the triplet lifetimes of the carbonyl chromophore (e.g., 1.6 versus 2.7 micros), has been found for these compounds. With an alkylaromatic moiety as donor, related effects have been observed, albeit strongly dependent on the length of the spacer. The reactivity trend for the initial hydrogen transfer step is paralleled by the quantum yields of the overall photoreaction. The biradicals, formed via remote hydrogen abstraction, undergo intramolecular recombination to macrocyclic ring systems. The new photoproducts have been isolated and characterized by NMR spectroscopy. The stereochemistry of the macrocycles, which contain up to four asymmetric carbons, has been unambiguously assigned on the basis of single-crystal structures and/or NOE effects. Interestingly, a highly regio- and stereoselective macrocyclization has been found for the ketoprofen-tetrahydrofuran conjugates, where hydrogen abstraction from the less substituted carbon is exclusive; cisoid ring junction is always preferred over the transoid junction. The photoreaction is less regioselective for compounds with an isopropylbenzene residue. The reactivity and selectivity trends have been rationalized by DFT (B3LYP/6-31G*) calculations.     

Molecular structure and reactivity of titania-supported transition metal oxide catalysts synthesized by equilibrium deposition filtration for the oxidative dehydrogenation of ethane

The molecular structure and catalytic performance of (MoO_x)_n/TiO₂, (WO_x)_n/TiO₂ and (VO_x)_n/TiO₂ catalysts (synthesized by the equilibrium–deposition–filtration/EDF method) for oxidative dehydrogenation (ODH) of ethane were studied by in situ Raman spectroscopy at 430 °C and catalytic measurements in the temperature range of 420–480 °C. The extent of association within the deposited oxometallic phase followed the sequence (VO_x)_n/TiO₂ >> (MoO_x)_n/TiO₂ > (WO_x)_n/TiO₂; a concurrent trend in reduction susceptibility was evidenced by exploiting the relative normalized Raman band intensities while monitoring the response of the vibrational properties of the catalytic samples under reactive (C₂H₆/O₂/He) and reducing (C₂H₆/He) conditions by in situ Raman spectroscopy. The catalyst reactivity tracks the corresponding trend in reduction susceptibility as evidenced by the in situ Raman spectra. Selective reaction pathways are favored at high coverage whilst combustion routes are activated at low coverages due to the involvement of carrier lattice oxygen sites. The observed apparent reaction rates and activation energies are discussed in relation to various structural and reactivity aspects.     

Switch in stereoselectivity caused by the isocyanide structure in the rhodium-catalyzed silylimination of alkynes

The reaction of terminal alkynes with hydrosilanes and tert-alkyl isocyanides in the presence of Rh(4)(CO)(12) gives (Z)-β-silyl-α,β-unsaturated imines in good yields. On the other hand, the use of aryl isocyanides in place of tert-alkyl isocyanides leads to the formation of E isomers.     

Evaluation of the kinetic data for intramolecular 1,x-hydrogen shifts in alkyl radicals and structure/reactivity predictions from the carbocyclic model for the transition state

Experimental and computational kinetic data for the intramolecular 1,x-hydrogen shift in alkyl radicals are compiled in Arrhenius format for x = 2-5. Significant experimental disparity remains, especially for x = 2 and 3. Experimental data for radicals with tert centers or bearing spectator substituents are lacking for all x, and none exist for x = 6. The common use of the strain energy of the unsubstituted (x+1)-carbocycle to coarsely model the activation energy for the 1,x-shift is extended to explore more subtle differences in progressively methyl-substituted systems by use of molecular mechanics estimates of differences in strain between radicals and carbocycles. For x = 5 and 6, a sterically driven increase in E is predicted for shifts in the tert --> tert class that apparently runs counter to the behavior of bimolecular hydrogen transfers. In contrast, a sterically driven decrease in E is predicted to result from spectator methyl groups for the prim --> prim reaction class for all x. There is no experimental basis to test these predictions; fragmentary computational evidence lends some support to the second but is ambiguous concerning the first. Possible deficiencies in the use of carbocycles as transition state models are discussed.     

Nucleophilic addition to C,C double bonds. III. Chemical reactivity of 1endo, 4endo: 5exo, 8exo-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalen-10syn-ol and X-ray structure analysis of its p-nitrobenzoate

The title compound 1 is a further example of an olefinic alcohol that undergoes ether formation under basic conditions (→ 3) although the double bond is not activated by an electron-attracting group. This unusual reactivity is due to steric compression, which is increased in the 10-methyl analogue 2. This forms the corresponding ether 7 at a much higher rate. - In a deuteriated medium, base-catalysed cyclization of 1 gives the exo-deuteriated ether 6 , corresponding to trans-addition. - An X-ray structure analysis of 4 , the p-nitrobenzoate of 1 , is presented.     

Electronic structure and reactivity of guanylthiourea: A quantum chemical study

Electronic structure analysis of guanylthiourea (GTU) and its isomers has been carried out using quantum chemical methods. Two major tautomeric classes (thione and thiol) have been identified on the potential energy (PE) surface. In both the cases conjugation of pi‐electrons and intramolecular H‐bonds have been found to play a stabilizing role. Various isomers of GTU on its PE surface have been analyzed in two different groups (thione and thiol). The interconversion from the most stable thione conformer ( GTU‐1 ) to the most stable thiol conformer ( GTU‐t1 ) was found to take place via bimolecular process which involves protonation at sulfur atom of GTU‐1 followed by subsequent C? N bond rotation and deprotonation. The detailed analysis of the protonation has been carried out in gas phase and aqueous phase (using CPMC model). Sulfur atom (S1) was found to be the preferred protonation site (over N4) in GTU‐1 in gas phase whereas N4 was found to be the preferred site of protonation in aqueous medium. The mechanism of S‐alkylation reaction in GTU has also been studied. The formation of alkylated analogs of thiol isomers (alkylated guanylthiourea) is believed to take place via bimolecular process which involves alkyl cation attack at S atom followed by C? N bond rotation and deprotonation. The reactive intermediate RS(NH₂)C? N? C(NH₂)₂⁺ belongs to the newly identified ^⊕N(←L)₂ class of species and provides the necessary dynamism for easy conversion of thione to thiol. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010