Enol Formation and Ring-Opening in OH-Initiated Oxidation of Cycloalkenes

2008 ◽  
Vol 112 (51) ◽  
pp. 13444-13451 ◽  
Author(s):  
Giovanni Meloni ◽  
Talitha M. Selby ◽  
David L. Osborn ◽  
Craig A. Taatjes
Keyword(s):  
Ring Opening ◽  
Enol Formation

Amino-functional polyethers: versatile, stimuli-responsive polymers

2020 ◽  
Vol 11 (24) ◽  
pp. 3940-3950 ◽  
Author(s):  
Patrick Verkoyen ◽  
Holger Frey
Keyword(s):  
Ring Opening ◽  
Review Article ◽  
Stimuli Responsive ◽  
New Class ◽  
Stimuli Responsive Polymers ◽  
Responsive Polymers

Amino-functional polyethers have emerged as a new class of “smart”, i.e. pH- and thermoresponsive materials. This review article summarizes the synthesis and applications of these materials, obtained from ring-opening of suitable epoxide monomers.

Reversible Oxidative-Addition and Reductive-Elimination of Thiophene from a Titanium Complex and Its Thermally-Induced Hydrodesulfurization Chemistry

2019 ◽  
Author(s):  
Alejandra Gomez-Torres ◽  
J. Rolando Aguilar-Calderón ◽  
Carlos Saucedo ◽  
Aldo Jordan ◽  
Alejandro J. Metta-Magaña ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Ring Opening ◽  
Thiophene Ring ◽  
Oxidative Addition ◽  
Reductive Elimination ◽  
Thermally Induced ◽  
Titanium Complex

<p>The masked Ti(II) synthon (<sup>Ket</sup>guan)(<i>η</i><sup>6</sup>-Im<sup>Dipp</sup>N)Ti (<b>1</b>) oxidatively adds across thiophene to give ring-opened (<sup>Ket</sup>guan)(Im<sup>Dipp</sup>N)Ti[<i>κ</i><sup>2</sup>-<i>S</i>(CH)<sub>3</sub><i>C</i>H] (<b>2</b>). Complex <b>2</b> is photosensitive, and upon exposure to light, reductively eliminates thiophene to regenerate <b>1</b> – a rare example of early-metal mediated oxidative-addition/reductive-elimination chemistry. DFT calculations indicate strong titanium π-backdonation to the thiophene π*-orbitals leads to the observed thiophene ring opening across titanium, while a proposed photoinduced LMCT promotes the reverse thiophene elimination from <b>2</b>. Finally, pressurizing solutions of <b>2 </b>with H<sub>2</sub> (150 psi) at 80 °C leads to the hydrodesulfurization of thiophene to give the Ti(IV) sulfide (<sup>Ket</sup>guan)(Im<sup>Dipp</sup>N)Ti(S) (<b>3</b>) and butane. </p>

Visible Light-Promoted Catalytic Ring-Opening Isomerization of 1,2-Disubstituted Cyclopropanols to Linear Ketones

2019 ◽  
Author(s):  
Marharyta V. Laktsevich-Iskryk ◽  
Nastassia A. Varabyeva ◽  
Volha V. Kazlova ◽  
Vladimir N. Zhabinskii ◽  
Vladimir A. Khripach ◽  
...  
Keyword(s):  
Visible Light ◽  
Functional Groups ◽  
Ring Opening ◽  
Radical Intermediates ◽  
Reaction Proceeds

In this article, we report a photocatalytic protocol for the isomerization of 1,2-disubstituted cyclopropanols to linear ketones. The reaction proceeds <i>via</i> radical intermediates and tolerates various functional groups.

Visible Light-Promoted Catalytic Ring-Opening Isomerization of 1,2-Disubstituted Cyclopropanols to Linear Ketones

2019 ◽  
Author(s):  
Marharyta V. Laktsevich-Iskryk ◽  
Nastassia A. Varabyeva ◽  
Volha V. Kazlova ◽  
Vladimir N. Zhabinskii ◽  
Vladimir A. Khripach ◽  
...  
Keyword(s):  
Visible Light ◽  
Functional Groups ◽  
Ring Opening ◽  
Radical Intermediates ◽  
Reaction Proceeds

In this article, we report a photocatalytic protocol for the isomerization of 1,2-disubstituted cyclopropanols to linear ketones. The reaction proceeds <i>via</i> radical intermediates and tolerates various functional groups.

A Recommender System for Inverse Design of Polycarbonates and Polyesters

2020 ◽  
Author(s):  
Nathaniel Park ◽  
Dmitry Yu. Zubarev ◽  
James L. Hedrick ◽  
Vivien Kiyek ◽  
Christiaan Corbet ◽  
...  
Keyword(s):  
Ring Opening ◽  
High Performance ◽  
Recommendation System ◽  
Polymeric Materials ◽  
Monomer Conversion ◽  
Design Strategy ◽  
Ring Opening Polymerization ◽  
Inverse Design ◽  
False Negatives ◽  
Accelerate Development

The convergence of artificial intelligence and machine learning with material science holds significant promise to rapidly accelerate development timelines of new high-performance polymeric materials. Within this context, we report an inverse design strategy for polycarbonate and polyester discovery based on a recommendation system that proposes polymerization experiments that are likely to produce materials with targeted properties. Following recommendations of the system driven by the historical ring-opening polymerization results, we carried out experiments targeting specific ranges of monomer conversion and dispersity of the polymers obtained from cyclic lactones and carbonates. The results of the experiments were in close agreement with the recommendation targets with few false negatives or positives obtained for each class.<br>

Endgroup and Sidechain Functionalization of Surface-Initiated ROMP Thin Films: Progress Towards ROMP-Based Molecular Wires

2018 ◽  
Author(s):  
Nicholas Marshall
Keyword(s):  
Thin Films ◽  
Contact Angle ◽  
Cyclic Voltammetry ◽  
Polymer Films ◽  
Conjugated Polymer ◽  
Ring Opening ◽  
Molecular Wires ◽  
Metathesis Polymerization ◽  
Cross Metathesis ◽  
Active Ester

A set of experiments in surface-initiated ring-opening metathesis polymerization, including end-functionalization of growing brushes and contact angle/cyclic voltammetry measurements. We report preparation and CV of two different conjugated polymer films, and several endgroup and sidechain functionalization experiments using cross-metathesis and active ester substitution.<br>

On the Conrotatory Ring Opening of 3-Carbomethoxycyclobutene Vis-À-Vis 3-Carbomethoxy-1,2-Benzocyclobutene and the Predominant Inward Opening of 3-Dimethylaminocarbonyl-1,2-Benzocyclobutene

2018 ◽  
Author(s):  
Veejendra Yadav ◽  
Dasari L V K Prasad ◽  
Arpita Yadav ◽  
Maddali L N Rao
Keyword(s):  
Transition State ◽  
Ring Opening ◽  
Electron Process ◽  
Ring Opening Reaction ◽  
Stable Species ◽  
Electron Event

<p>The torquoselectivity of conrotatory ring opening of 3-carbomethoxycyclobutene is controlled by p<sub>C1C2</sub>→s*<sub>C3C4</sub> and s<sub>C3C4</sub>→p*<sub>CO</sub> interactions in the transition state in a 4-electron process as opposed to only s<sub>C3C4</sub>→p*<sub>CO</sub> interaction in an apparently 8-electron event in 3-carbomethoxy-1,2-benzocyclobutene. The ring opening of 3-carbomethoxy-1,2-benzocyclobutene is sufficiently endothermic. We therefore argue that the reverse ring closing reaction is faster than the forward ring opening reaction and, thus, it establishes an equilibrium between the two and subsequently allows formation of the more stable species <i>via</i> outward ring opening reaction. Application of this argument to 3-dimethylaminocarbonyl-1,2-benzocyclobutene explains the predominantly observed inward opening.</p>

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