Andrei Vedernikov | University of Maryland, College Park (original) (raw)
Papers by Andrei Vedernikov
Journal of the American Chemical Society, Jan 26, 2008
ABSTRACT Internal olefins, cis-cyclooctene and norbornene, react with (dpms)Pt-II(OH)(ethene) in ... more ABSTRACT Internal olefins, cis-cyclooctene and norbornene, react with (dpms)Pt-II(OH)(ethene) in water to produce Pt-II oxetanes (norbornene) or hydroxo olefin complexes (cis-cyclooctene); both produce anionic Pt-II oxetanes in basic solutions; their subsequent aerobic oxidation cleanly furnishes corresponding Pt-II oxetanes that undergo direct C(sp(3))-O reductive elimination of olefin oxides in various solvents and in the solid-state that is unprecedented for Pt-IV.
Organic Letters, Jul 19, 2023
Angewandte Chemie, Oct 31, 2002
RSC catalysis series, Jun 17, 2013
High-valent organopalladium(iv) chemistry has found many practical applications in catalytic oxid... more High-valent organopalladium(iv) chemistry has found many practical applications in catalytic oxidative functionalization of organic substrates. A number of important functional groups can be introduced into an organic molecule using C–X reductive elimination from the palladium(iv) center. A great variety of oxidants can be used to convert low-valent organopalladium species into their high-valent derivatives. Though our analysis was limited mostly to the cases of oxidative C–H functionalization, many other methods exist that allow the introduction of a hydrocarbyl ligand into the palladium(ii) coordination sphere. One can imagine that in some near future an even greater variety of C–X elimination reactions from palladium(iv) centers will be disclosed and, not less importantly, less expensive and environmentally more benign reagents will be used to achieve conversion of organopalladium(ii) species to their high-valent organopalladium derivatives. The latter may become possible as we improve our currently very limited understanding of mechanisms of oxidation of organopalladium(ii) complexes. Finally, the success of high-valent organopalladium chemistry boosted by new demanding practical applications of synthetic organic chemistry might lead to exploration and extensive growth of high-valent organometallic chemistry of some other transition metals.
Handbook of CH‐Functionalization, Oct 1, 2022
Journal of Organometallic Chemistry, Feb 1, 2019
Reactivity of K 2 [Pt IV CH 3 Cl 5 ] toward a series of substituted N,N-dimethylanilines 1a-1g, N... more Reactivity of K 2 [Pt IV CH 3 Cl 5 ] toward a series of substituted N,N-dimethylanilines 1a-1g, N,Ndiisopropylaniline 1h and 2,6-substituted pyridines 2a-2b was investigated in 60% (vol.) aqueous acetone solutions. The reactions result in corresponding N-methylammonium or Nmethylpyridinium products, 3 or 4, with high selectivity for the substrates 1a-1g and 2b, and follow an overall 2 nd order kinetics, 1 st order in both the Pt IV complex and the amines. The reactivity is discussed in terms of the amine electronic properties and steric bulk. For the series of N,N-dimethylanilines 1a-1g, Me 2 NC 6 H 4 R (R = H, m-Cl, p-Cl, m-Me, p-Me, p-MeO, p-Me 2 N), a high quality linear correlation was found between logarithm of the reaction second order rate constant, log(k 2), and pK a of the anilines. At the same time, the reactivity of the bulkier N,N-diisopropylaniline substrate 1h is about 3 orders of magnitude lower than predicted using this correlation. Finally, the pyridines 2a-2b are 3-4 orders of magnitude less reactive than N,Ndimethylanilines of similar pK a. Interestingly, the reactivity of K 2 [Pt IV CH 3 Cl 5 ] toward N,Ndimethylanilines is of the same order of magnitude or slightly greater than that of a standard organic methylating agent, dimethylsulfate Me 2 SO 4. A computational (DFT) modeling of the title reaction is consistent with the formation of five-coordinate Pt IV Me electrophile, [Pt IV CH 3 Cl 4 ]-, which is involved in S N 2 attack at its methyl group carbon by nucleophilic amines.
The empirical Pauling equation was used to develop a simple qualitative model for the description... more The empirical Pauling equation was used to develop a simple qualitative model for the description and prediction of the thermodynamic substrate and regioselectivities of alkane reactions with carbenes, nitrenes, oxene, halogens, and metal complexes. The feasibility of the model was demonstrated on examples of isomerization and transfunctionalization reactions of alkyl halides, alcohols, thiols, primary amines, and nitro compounds. A sequence
ChemInform, Dec 2, 2008
Catalytic Aerobic Oxidation and Tandem Enantioselective Cycloaddition in Cascade Multicomponent S... more Catalytic Aerobic Oxidation and Tandem Enantioselective Cycloaddition in Cascade Multicomponent Synthesis.-Copper catalyzed aerobic oxidation of cyclopentadiene to cyclopentadienone and subsequent asymmetric 1,3-dipolar cycloaddition of azomethine ylides produces tricyclic ketones with excellent diastereo-and enantioselectivities.-(
ChemInform, Aug 20, 2010
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was e... more ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Journal of Hazardous Materials
Thirty four (hetero)arene derivatives have been tested in catalytic H/D exchange reactions involv... more Thirty four (hetero)arene derivatives have been tested in catalytic H/D exchange reactions involving their C(sp2)–H bonds and 2,2,2-trifluoroethanol-d1 (TFE-d1) in the presence of the homogeneous P...
An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
ACS Catalysis, 2016
We report platinum catalysts for the efficient aerobic oxidation of olefins to form epoxides and/... more We report platinum catalysts for the efficient aerobic oxidation of olefins to form epoxides and/or derived glycol monoethers. The catalystsdiaqua and dichloro Pt II complexes supported by the ligand di(2-pyridine)methanesulfonate (dpms)are most active when they are covalently tethered to mesoporous silica nanoparticles (MSNs). Supporting the molecular Pt complexes on the MSNs prevents bimolecular catalyst deactivation. Using this strategy, >40 000 turnovers are achieved for the aerobic oxidation of norbornene in 2,2,2-trifluoroethanol. The position of the tether and the nature of other ligands in the metal coordination sphere (aqua, hydroxo, or chloro) are shown to affect the catalyst activity. The new MSN-supported Pt materials were characterized by nuclear magnetic resonance (NMR) spectroscopy, nitrogen physisorption, powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA).
Chemical Science, 2021
Di(2-pyridyl)ketone dimethylplatinum(ii), (dpk)PtII(CH3)2, reacts with CD3OD at 25 °C to undergo ... more Di(2-pyridyl)ketone dimethylplatinum(ii), (dpk)PtII(CH3)2, reacts with CD3OD at 25 °C to undergo complete deuteration of Pt–CH3 fragments in ∼5 h without loss of methane to form (dpk)PtII(CD3)2 in virtually quantitative yield.
Journal of the American Chemical Society, Jan 26, 2008
ABSTRACT Internal olefins, cis-cyclooctene and norbornene, react with (dpms)Pt-II(OH)(ethene) in ... more ABSTRACT Internal olefins, cis-cyclooctene and norbornene, react with (dpms)Pt-II(OH)(ethene) in water to produce Pt-II oxetanes (norbornene) or hydroxo olefin complexes (cis-cyclooctene); both produce anionic Pt-II oxetanes in basic solutions; their subsequent aerobic oxidation cleanly furnishes corresponding Pt-II oxetanes that undergo direct C(sp(3))-O reductive elimination of olefin oxides in various solvents and in the solid-state that is unprecedented for Pt-IV.
Organic Letters, Jul 19, 2023
Angewandte Chemie, Oct 31, 2002
RSC catalysis series, Jun 17, 2013
High-valent organopalladium(iv) chemistry has found many practical applications in catalytic oxid... more High-valent organopalladium(iv) chemistry has found many practical applications in catalytic oxidative functionalization of organic substrates. A number of important functional groups can be introduced into an organic molecule using C–X reductive elimination from the palladium(iv) center. A great variety of oxidants can be used to convert low-valent organopalladium species into their high-valent derivatives. Though our analysis was limited mostly to the cases of oxidative C–H functionalization, many other methods exist that allow the introduction of a hydrocarbyl ligand into the palladium(ii) coordination sphere. One can imagine that in some near future an even greater variety of C–X elimination reactions from palladium(iv) centers will be disclosed and, not less importantly, less expensive and environmentally more benign reagents will be used to achieve conversion of organopalladium(ii) species to their high-valent organopalladium derivatives. The latter may become possible as we improve our currently very limited understanding of mechanisms of oxidation of organopalladium(ii) complexes. Finally, the success of high-valent organopalladium chemistry boosted by new demanding practical applications of synthetic organic chemistry might lead to exploration and extensive growth of high-valent organometallic chemistry of some other transition metals.
Handbook of CH‐Functionalization, Oct 1, 2022
Journal of Organometallic Chemistry, Feb 1, 2019
Reactivity of K 2 [Pt IV CH 3 Cl 5 ] toward a series of substituted N,N-dimethylanilines 1a-1g, N... more Reactivity of K 2 [Pt IV CH 3 Cl 5 ] toward a series of substituted N,N-dimethylanilines 1a-1g, N,Ndiisopropylaniline 1h and 2,6-substituted pyridines 2a-2b was investigated in 60% (vol.) aqueous acetone solutions. The reactions result in corresponding N-methylammonium or Nmethylpyridinium products, 3 or 4, with high selectivity for the substrates 1a-1g and 2b, and follow an overall 2 nd order kinetics, 1 st order in both the Pt IV complex and the amines. The reactivity is discussed in terms of the amine electronic properties and steric bulk. For the series of N,N-dimethylanilines 1a-1g, Me 2 NC 6 H 4 R (R = H, m-Cl, p-Cl, m-Me, p-Me, p-MeO, p-Me 2 N), a high quality linear correlation was found between logarithm of the reaction second order rate constant, log(k 2), and pK a of the anilines. At the same time, the reactivity of the bulkier N,N-diisopropylaniline substrate 1h is about 3 orders of magnitude lower than predicted using this correlation. Finally, the pyridines 2a-2b are 3-4 orders of magnitude less reactive than N,Ndimethylanilines of similar pK a. Interestingly, the reactivity of K 2 [Pt IV CH 3 Cl 5 ] toward N,Ndimethylanilines is of the same order of magnitude or slightly greater than that of a standard organic methylating agent, dimethylsulfate Me 2 SO 4. A computational (DFT) modeling of the title reaction is consistent with the formation of five-coordinate Pt IV Me electrophile, [Pt IV CH 3 Cl 4 ]-, which is involved in S N 2 attack at its methyl group carbon by nucleophilic amines.
The empirical Pauling equation was used to develop a simple qualitative model for the description... more The empirical Pauling equation was used to develop a simple qualitative model for the description and prediction of the thermodynamic substrate and regioselectivities of alkane reactions with carbenes, nitrenes, oxene, halogens, and metal complexes. The feasibility of the model was demonstrated on examples of isomerization and transfunctionalization reactions of alkyl halides, alcohols, thiols, primary amines, and nitro compounds. A sequence
ChemInform, Dec 2, 2008
Catalytic Aerobic Oxidation and Tandem Enantioselective Cycloaddition in Cascade Multicomponent S... more Catalytic Aerobic Oxidation and Tandem Enantioselective Cycloaddition in Cascade Multicomponent Synthesis.-Copper catalyzed aerobic oxidation of cyclopentadiene to cyclopentadienone and subsequent asymmetric 1,3-dipolar cycloaddition of azomethine ylides produces tricyclic ketones with excellent diastereo-and enantioselectivities.-(
ChemInform, Aug 20, 2010
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was e... more ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Journal of Hazardous Materials
Thirty four (hetero)arene derivatives have been tested in catalytic H/D exchange reactions involv... more Thirty four (hetero)arene derivatives have been tested in catalytic H/D exchange reactions involving their C(sp2)–H bonds and 2,2,2-trifluoroethanol-d1 (TFE-d1) in the presence of the homogeneous P...
An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
ACS Catalysis, 2016
We report platinum catalysts for the efficient aerobic oxidation of olefins to form epoxides and/... more We report platinum catalysts for the efficient aerobic oxidation of olefins to form epoxides and/or derived glycol monoethers. The catalystsdiaqua and dichloro Pt II complexes supported by the ligand di(2-pyridine)methanesulfonate (dpms)are most active when they are covalently tethered to mesoporous silica nanoparticles (MSNs). Supporting the molecular Pt complexes on the MSNs prevents bimolecular catalyst deactivation. Using this strategy, >40 000 turnovers are achieved for the aerobic oxidation of norbornene in 2,2,2-trifluoroethanol. The position of the tether and the nature of other ligands in the metal coordination sphere (aqua, hydroxo, or chloro) are shown to affect the catalyst activity. The new MSN-supported Pt materials were characterized by nuclear magnetic resonance (NMR) spectroscopy, nitrogen physisorption, powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA).
Chemical Science, 2021
Di(2-pyridyl)ketone dimethylplatinum(ii), (dpk)PtII(CH3)2, reacts with CD3OD at 25 °C to undergo ... more Di(2-pyridyl)ketone dimethylplatinum(ii), (dpk)PtII(CH3)2, reacts with CD3OD at 25 °C to undergo complete deuteration of Pt–CH3 fragments in ∼5 h without loss of methane to form (dpk)PtII(CD3)2 in virtually quantitative yield.