Implications of the final ring closure to 10b-aza-10c-borapyrene for aryl–alkyne ring-closing mechanisms

2017 ◽  
Vol 95 (4) ◽  
pp. 357-362 ◽  
Author(s):  
Joseph A. Jaye ◽  
Benjamin S. Gelinas ◽  
Grant M. McCormick ◽  
Eric H. Fort
Keyword(s):  
Activation Energy ◽  
Functional Groups ◽  
Isotopic Labeling ◽  
Ring Closure ◽  
Synthetic Methods ◽  
Reaction Conditions ◽  
Fused Ring ◽  
Reaction Proceeds ◽  
Efficient Construction ◽  
Alternate Mechanism

Through a combined computational and isotopic labeling study, it has been observed that the activation energy for the aryl–alkyne ring closure of the azaborine containing 4-ethynyl-4a-aza-4b-boraphenanthrene is dramatically lower, and it appears to proceed via an alternate mechanism than that of its hydrocarbon analog. This catalyst-free reaction proceeds at modest reaction conditions compared with traditional pyrolytic synthetic methods and holds promise for the efficient construction of fused ring systems containing azaborine functional groups that may not be accessible in the purely hydrocarbon form.

Catalytic Sulfone Upgrading Reaction with Alcohols via Ru(II)

2019 ◽  
Author(s):  
Tomas Vojkovsky ◽  
Shubham Deolka ◽  
Saiyyna P. Stepanova ◽  
Michael C. Roy ◽  
Eugene Khaskin
Keyword(s):  
Functional Groups ◽  
Secondary Alcohol ◽  
Value Added ◽  
Catalytic Dehydrogenation ◽  
Reaction Conditions ◽  
Stoichiometric Amount ◽  
Reaction Proceeds ◽  
One Step ◽  
Value Added Products

<a>Sulfones and sulfonamides with an α-CH bond can be easily alkylated by aliphatic alcohols to add the carbon skeleton of the alcohol via a one-step, Ru(II) catalyzed redox neutral reaction. The reaction requires a sub-stoichiometric amount of base and produces only water as a byproduct. A number of pharmaceutically relevant functional groups such as piperidine, morpholine, etc. are well tolerated under the reaction conditions to give higher value-added products in one step from widely available substrates. The reaction proceeds through a sulfone carbanion addition to an in-situ generated aldehyde formed via catalytic dehydrogenation and subsequent catalyst mediated replacement of the secondary alcohol by hydrogen.</a>

Catalytic Sulfone Upgrading Reaction with Alcohols via Ru(II)

2019 ◽  
Author(s):  
Tomas Vojkovsky ◽  
Shubham Deolka ◽  
Saiyyna P. Stepanova ◽  
Michael C. Roy ◽  
Eugene Khaskin
Keyword(s):  
Functional Groups ◽  
Secondary Alcohol ◽  
Value Added ◽  
Catalytic Dehydrogenation ◽  
Reaction Conditions ◽  
Stoichiometric Amount ◽  
Reaction Proceeds ◽  
One Step ◽  
Value Added Products

<a>Sulfones and sulfonamides with an α-CH bond can be easily alkylated by aliphatic alcohols to add the carbon skeleton of the alcohol via a one-step, Ru(II) catalyzed redox neutral reaction. The reaction requires a sub-stoichiometric amount of base and produces only water as a byproduct. A number of pharmaceutically relevant functional groups such as piperidine, morpholine, etc. are well tolerated under the reaction conditions to give higher value-added products in one step from widely available substrates. The reaction proceeds through a sulfone carbanion addition to an in-situ generated aldehyde formed via catalytic dehydrogenation and subsequent catalyst mediated replacement of the secondary alcohol by hydrogen.</a>

Chalcogenative spirocyclization of N-aryl propiolamides with diselenides/disulfides promoted by Selectfluor

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Jin-Wei Yuan ◽  
Guang-Chao Huang ◽  
Li-Li Wang ◽  
Xin-Yuan Wang ◽  
Liang-Ru Yang ◽  
...  
Keyword(s):  
Functional Groups ◽  
Synthetic Route ◽  
Reaction Conditions ◽  
Triple Bonds ◽  
Wide Range ◽  
Reaction Proceeds

Abstract A practical and efficient synthetic route to construct a variety of 3-arylselenenyl/3-arylthio spiro[4.5]trienones was developed using Selectfluor reagent as a mild oxidant. This reaction proceeds via a sequence of electrophilic cation addition, spirocyclization and dearomatization, then offers an approach to introduce Se/S-centered cation into the C–C triple bonds. The utility of this protocol were justified by the excellent compatibility of a wide range of functional groups, good yields and scalability under mild reaction conditions.

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.

Chemical reduction of chlorpyrifos driven by flavin mononucleotide functionalized titanium (IV) dioxide

2020 ◽  
Vol 5 (11) ◽  
Author(s):  
Stephanie Santos Díaz ◽  
Hazim Al-Zubaidi ◽  
Amir C. Ross-Obare ◽  
Sherine O. Obare
Keyword(s):  
Functional Groups ◽  
Organic Contaminants ◽  
Chemical Reduction ◽  
Flavin Mononucleotide ◽  
Reaction Conditions ◽  
Organophosphate Compounds ◽  
Biological Molecule ◽  
Highly Active ◽  
New Directions ◽  
Detrimental Impact

AbstractFor many decades, organohalide and organophosphate compounds have shown significant detrimental impact on the environment. Consequently, strategies for their remediation continue to be an area of emerging need. The reduction of the chlorpyrifos pesticide, a molecule that bears both organohalide and organophosphate functional groups, is an important area of investigation due to it toxic nature. In this report, we demonstrate the effectiveness of the biological molecule, flavin mononucleotide (FMN) toward chemically reducing chlorpyrifos. The FMN was found to be highly active when anchored to nanocrystalline TiO2 surfaces. The results show new directions toward the remediation of organic contaminants under mild reaction conditions.

Regiospecific preparation of 10-allyl-1-ketoquinolizidine and an unexpected disproportionation during its Wolff–Kischner reduction

1979 ◽  
Vol 57 (16) ◽  
pp. 2114-2117 ◽  
Author(s):  
John M. McIntosh
Keyword(s):  
Ring System ◽  
Sigmatropic Rearrangement ◽  
High Yield ◽  
Reaction Conditions ◽  
Fused Ring ◽  
Fused Ring System

Regiospecific formation of 10-allyl-1-ketoquinolizidine (7) is achieved in high yield by a [2.3] sigmatropic rearrangement of N-allyl-1-ketoquinolizidinium bromide (6). Wolff–Kischner reduction of 7 affords 10-allylquinolizidine (8) contaminated by the 10-propyl and 10-ethynyl analogs in amounts which depend on the reaction conditions. The carbon-13 spectrum of 8 indicates a trans-fused ring system with an axial substituent at C-10.

Kinetic Model of the 1,2-Propanediol Oxidation Reaction in the Presence of 3wt%Pd/α-Al2O3 Catalyst

2021 ◽  
Vol 903 ◽  
pp. 143-148
Author(s):  
Svetlana Cornaja ◽  
Svetlana Zhizhkuna ◽  
Jevgenija Vladiko
Keyword(s):  
Activation Energy ◽  
Lactic Acid ◽  
Kinetic Model ◽  
Catalytic Oxidation ◽  
Molecular Oxygen ◽  
Oxidation Reaction ◽  
Main Product ◽  
Oxidation Process ◽  
Water Solution ◽  
Reaction Conditions

Supported 3wt%Pd/α-Al₂O₃ catalyst was tested in selective oxidation of 1,2-propanediol by molecular oxygen. It was found that the catalyst is active in an alkaline water solution. Lactic acid was obtained as the main product of the reaction. Influence of different reaction conditions on 1,2-PDO conversion and oxidation process selectivity was studied. Partial kinetic orders of the reaction with respect to 1,2-propanediol, c0(NaOH), p(O2), n(1,2-PDO)/n(Pd)) were determined and an experimental kinetic model of the catalytic oxidation reaction was obtained. Activation energy of the process was calculated and was found to be about 53 ± 5 kJ/mol.

scholarly journals Preparation of Glucosamine Hydrochloride from Indigenous Shrimp Processing Waste

1970 ◽  
Vol 46 (3) ◽  
pp. 375-378 ◽  
Author(s):  
MM Islam ◽  
SM Masum ◽  
MM Rahman ◽  
AA Shaikh
Keyword(s):  
Maximum Yield ◽  
Therapeutic Activity ◽  
Processing Waste ◽  
Reaction Conditions ◽  
Glucosamine Hydrochloride ◽  
Glycoside Linkage ◽  
Shrimp Shell ◽  
Reaction Proceeds ◽  
Ft Ir ◽  
Hydrolysis Of

The present investigation described the effective preparation of glucosamine hydrochloride (GluHCl) from chitin which was extracted from indigenous shrimp shell. GluHCl has attracted much attention owing to its therapeutic activity in osteoarthritis and widely used dietary supplement. The key step involved was extraction of chitin from shrimp skeleton and then hydrolysis of chitin by concentrated hydrochloric acid. The reaction proceeds via break down of glycoside linkage. Structural analysis was carried out by melting point, TLC, FT-IR, elemental analysis and all the data were compared with that of standard GluHCl. The elemental (C, 32.75; H, 6.51; N, 6.20) analysis is good concord with the calculated value (C, 33.42; H, 6.54; N, 6.50). Absence of v max at 1726 cm-1 indicates that GluHCl is a deacetylated product of chitin. The yields of the product mainly depend on reaction conditions. Maximum yield (63.5%) was obtained when chitin was hydrolyzed with concentrated HCl for 1.30 h. Key words: Shrimp shell; Chitin, Acid hydrolysis; Glucosamine hydrochloride Osteoarthritis. DOI: http://dx.doi.org/10.3329/bjsir.v46i3.9046 BJSIR 2011; 46(3): 375-378

Sign in / Sign up

Export Citation Format

Share Document