Skeletal Rearrangements of Rings C and D of the Kaurene and Beyerene Tetracyclic Diterpenoids

2018 ◽  
Vol 42 (4) ◽  
pp. 175-180 ◽  
Author(s):  
James R. Hanson
Keyword(s):  
Reaction Pathway ◽  
Skeletal Rearrangement ◽  
Preferential Formation ◽  
Counter Ions ◽  
Carbonium Ions ◽  
Skeletal Rearrangements

The skeletal rearrangement of the bicyclo[3.2.1]octane portion of rings C and D of the kaurene and beyerene tetracyclic diterpenoids are reviewed, revealing the tendency of the secondary carbocations to rearrange to tertiary carbocations with the eventual preferential formation of bicyclo[2.2.2]octanes. Under acid-catalysed conditions the variations in the products with the nucleophilicity of the counter ions suggest that the intervention of discrete rather than completely delocalised non-classical carbonium ions may be contributing to the reaction pathway.

scholarly journals THE STEREOCHEMISTRY OF HALOGEN DISPLACEMENT BY NITRATE ION RACEMIZATION AND RETENTION OF CONFIGURATION IN THE SYNTHESIS OF DINITRATE ESTERS

1965 ◽  
Vol 43 (6) ◽  
pp. 1656-1660 ◽  
Author(s):  
L. D. Hayward ◽  
M. Jackson ◽  
I. G. Csizmadia
Keyword(s):  
Silver Nitrate ◽  
Steric Effect ◽  
Heterogeneous Reaction ◽  
Ion Pair ◽  
Alkyl Halides ◽  
Preferential Formation ◽  
Carbonium Ion ◽  
Carbonium Ions ◽  
And Inversion ◽  
Derivatives Of

The reaction of silver nitrate in dry acetonitrile with 2,5-dideoxy-2,5-diiodo-1,4;3,6-dianhydro-L-iditol resulted in formation of the dinitrate esters of the 1,4;3,6-dianhydrides of D-mannitol, D-glucitol, and L-iditol. Similarly both endo- and exo-nitrato groups were introduced in displacement of the endo-halogen in the 2-deoxy-2-iodo-5-O-acetyl and 2-deoxy-2-iodo-5-O-p-toluenesulfonyl derivatives of 1,4;3,6-dianhydro-L-iditol. Since both types of nitrato groups were stable to silver nitrate, the racemization occurred during the displacement and was attributed to formation of cyclic carbonium ion intermediates. The steric effect of the adjacent ring in the carbonium ions apparently suppressed the termolecular, ion-pair mechanism previously established for the metathesis of acyclic alkyl halides and caused preferential formation of the exo-nitrato derivatives.The heterogeneous reaction of meso-dibromostilbene with silver nitrate in acetic acid or acetonitrile gave meso-dihydrobenzoin dinitrate with overall retention of configuration. This result could be most readily reconciled with the contrasting sequence of retention and inversion previously reported for meso- and dl-2,3-dibromobutane if participation of neighboring phenyl groups occurred in the second displacement step.

BF3-Et2O mediated skeletal rearrangements of norbornyl appended cyclopentanediols

2015 ◽  
Vol 13 (9) ◽  
pp. 2768-2775 ◽  
Author(s):  
Chintada Nageswara Rao ◽  
Faiz Ahmed Khan
Keyword(s):  
Skeletal Rearrangement ◽  
Skeletal Rearrangements

Synthetically useful norbornyl appended cyclopentenones and pinacolone products are reported during the BF3-Et2O mediated skeletal rearrangement of norbornyl appended cyclopentanediols.

scholarly journals Isotopic labelling studies for a gold-catalysed skeletal rearrangement of alkynyl aziridines

2011 ◽  
Vol 7 ◽  
pp. 839-846 ◽  
Author(s):  
Paul W Davies ◽  
Nicolas Martin ◽  
Neil Spencer
Keyword(s):  
Skeletal Rearrangement ◽  
Rearrangement Product ◽  
Isotopic Labelling ◽  
Skeletal Rearrangements

Isotopic labelling studies were performed to probe a proposed 1,2-aryl shift in the gold-catalysed cycloisomerisation of alkynyl aziridines into 2,4-disubstituted pyrroles. Two isotopomers of the expected skeletal rearrangement product were identified using 13C-labelling and led to a revised mechanism featuring two distinct skeletal rearrangements. The mechanistic proposal has been rationalised against the reaction of a range of 13C- and deuterium-labelled substrates.

scholarly journals Clean Syn-Fuels via Hydrogenation Processes: Acidity–Activity Relationship in O-Xylene Hydrotreating

2020 ◽  
Vol 4 (1) ◽  
pp. 4 ◽  
Author(s):  
Alessandra Palella ◽  
Katia Barbera ◽  
Francesco Arena ◽  
Lorenzo Spadaro
Keyword(s):  
Reaction Pathway ◽  
Chemical Properties ◽  
Metal Sulfide ◽  
Acid Sites ◽  
Activity Relationship ◽  
Preferential Formation ◽  
Catalytic Materials ◽  
Type Zeolite ◽  
Environmental Requirement ◽  
Relationship Of

Transition metal sulfide catalysts are actually the most performing catalytic materials in crude oil hydrotreating (HDT), for energetic purposes. However, these systems suffer from several drawbacks that limit their exploitation. Aiming to meet the even more stringent environmental requirement, through a remarkable improvement of HDT performance in the presence of refractory feedstock (i.e., in terms of activity, selectivity, and stability), a deeper knowledge of the structure–activity relationship of catalysts must be achieved. Therefore, in this study, CoMo/γ-Al2O3 and NiMo/γ-Al2O3 catalysts were characterized and tested in the o-xylene hydrogenation model reaction, assessing the influence of both support acidity and catalyst acid strength on reaction pathway by employing γ-Al2O3 and Y-Type zeolite as acid reference materials. A clear relationship between concentration and strength of acid sites and the performance of the catalytic materials was established. Cobalt based catalyst (CoMoSx) proves a higher acidic character with respect to Nickel (NiMoSx), prompting isomerization reactions preferentially, also reflecting a greater o-xylene conversion. The different chemical properties of metals also affect the catalytic pathway, leading on the CoMoSx system to the preferential formation of p-xylene isomer with respect to m-xylene.

scholarly journals The synthetic substrate succinyl(carbadethia)-CoA generates cob(II)alamin on adenosylcobalamin-dependent methylmalonyl-CoA mutase

1993 ◽  
Vol 295 (2) ◽  
pp. 387-392 ◽  
Author(s):  
N H Keep ◽  
G A Smith ◽  
M C W Evans ◽  
G P Diakun ◽  
P F Leadlay
Keyword(s):  
Absorption Maximum ◽  
Reaction Pathway ◽  
Visible Spectrum ◽  
Skeletal Rearrangement ◽  
Visible Absorption ◽  
X Ray ◽  
Radical Intermediates ◽  
Synthetic Substrate ◽  
Simplified Procedure ◽  
X Ray Absorption

Succinyl(carbadethia)-coenzyme A, a synthetic substrate for adenosylcobalamin-dependent methylmalonyl-CoA mutase, has been prepared by a simplified procedure. When recombinant mutase was mixed with the synthetic substrate, the u.v./visible absorption spectrum of the bound cofactor changed rapidly to resemble that of cob(II)alamin, with an absorption maximum at 467 nm. Addition of the natural substrates, in contrast, produced only minor changes in the u.v./visible spectrum. The recent report of the generation of a complex e.p.r. spectrum on addition of substrate to the holo-methylmalonyl-CoA mutase was confirmed with the recombinant enzyme. The signals observed were stronger when the succinyl(carbadethia) analogue was used. Cobalt K-edge X-ray absorption spectroscopy confirmed that the addition of this analogue to holoenzyme leads to the generation of a cob(II)alamin-like species. These results strongly support the generation of cob(II)alamin during the 1,2-skeletal rearrangement catalysed by methylmalonyl-CoA mutase, as required if this enzyme follows the reaction pathway involving radical intermediates previously proposed for other adenosylcobalamin-dependent enzymes.

Catalytic Resonance Theory: Parallel Reaction Pathway Control

2019 ◽  
Author(s):  
M. Alexander Ardagh ◽  
Manish Shetty ◽  
Anatoliy Kuznetsov ◽  
Qi Zhang ◽  
Phillip Christopher ◽  
...  
Keyword(s):  
Chemical Reactions ◽  
Active Site ◽  
Active Sites ◽  
Reaction Pathway ◽  
Control Strategies ◽  
Oscillation Amplitude ◽  
Catalytic Performance ◽  
Parallel Reaction ◽  
Resonance Theory ◽  
Static Conditions

Catalytic enhancement of chemical reactions via heterogeneous materials occurs through stabilization of transition states at designed active sites, but dramatically greater rate acceleration on that same active site is achieved when the surface intermediates oscillate in binding energy. The applied oscillation amplitude and frequency can accelerate reactions orders of magnitude above the catalytic rates of static systems, provided the active site dynamics are tuned to the natural frequencies of the surface chemistry. In this work, differences in the characteristics of parallel reactions are exploited via selective application of active site dynamics (0 < ΔU < 1.0 eV amplitude, 10<sup>-6</sup> < f < 10<sup>4</sup> Hz frequency) to control the extent of competing reactions occurring on the shared catalytic surface. Simulation of multiple parallel reaction systems with broad range of variation in chemical parameters revealed that parallel chemistries are highly tunable in selectivity between either pure product, even when specific products are not selectively produced under static conditions. Two mechanisms leading to dynamic selectivity control were identified: (i) surface thermodynamic control of one product species under strong binding conditions, or (ii) catalytic resonance of the kinetics of one reaction over the other. These dynamic parallel pathway control strategies applied to a host of chemical conditions indicate significant potential for improving the catalytic performance of many important industrial chemical reactions beyond their existing static performance.

A Paramedic Treatment for Modeling Explicitly Solvated Chemical Reaction Mechanisms

2018 ◽  
Author(s):  
Yasemin Basdogan ◽  
John Keith
Keyword(s):  
Reaction Mechanism ◽  
Chemical Reaction ◽  
Reaction Mechanisms ◽  
Reaction Pathway ◽  
Optimization Procedure ◽  
Cost Effective ◽  
Chemical Reaction Mechanisms ◽  
Solvent Molecules ◽  
Dynamics Simulations ◽  
Mbh Reaction

<div> <div> <div> <p>We report a static quantum chemistry modeling treatment to study how solvent molecules affect chemical reaction mechanisms without dynamics simulations. This modeling scheme uses a global optimization procedure to identify low energy intermediate states with different numbers of explicit solvent molecules and then the growing string method to locate sequential transition states along a reaction pathway. Testing this approach on the acid-catalyzed Morita-Baylis-Hillman (MBH) reaction in methanol, we found a reaction mechanism that is consistent with both recent experiments and computationally intensive dynamics simulations with explicit solvation. In doing so, we explain unphysical pitfalls that obfuscate computational modeling that uses microsolvated reaction intermediates. This new paramedic approach can promisingly capture essential physical chemistry of the complicated and multistep MBH reaction mechanism, and the energy profiles found with this model appear reasonably insensitive to the level of theory used for energy calculations. Thus, it should be a useful and computationally cost-effective approach for modeling solvent mediated reaction mechanisms when dynamics simulations are not possible. </p> </div> </div> </div>

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