A5059399986- Asymmetric Hydrogenation and Catalysis
- Organometallic Complex Synthesis and Catalysis
- Synthetic Organic Chemistry Methods
- Oxidative Organic Chemistry Reactions
- Catalysis and Oxidation Reactions
- Asymmetric Synthesis and Catalysis
- Polyoxometalates: Synthesis and Applications
- Chemical Synthesis and Analysis
- Metal-Catalyzed Oxygenation Mechanisms
- Amino Acid Enzymes and Metabolism
- Radioactive element chemistry and processing
- Chemical Synthesis and Reactions
- Carbohydrate Chemistry and Synthesis
- Carbon dioxide utilization in catalysis
- Inorganic Chemistry and Materials
- Inorganic and Organometallic Chemistry
- Organic Chemistry Cycloaddition Reactions
- Microbial Community Ecology and Physiology
- Radiopharmaceutical Chemistry and Applications
- Ferrocene Chemistry and Applications
- Polyamine Metabolism and Applications
- Cyclopropane Reaction Mechanisms
- Lanthanide and Transition Metal Complexes
- Catalytic C–H Functionalization Methods
- Biological and pharmacological studies of plants
Oregon State University
2000-2023
Scripps Research Institute
1997
Cornell University
1989
Electronic effects in osmylation reactions accelerated by pyridine and quinuclidine derivatives were investigated varying the substituents on amine ligand as well alkene substrate. Ligand substituent gauged determination of equilibrium constants for coordination amines to OsO4, evaluation structural properties reduction potentials amine−OsO4 complexes, analysis kinetics osmylations presence amines. Substrate kinetic Hammett studies using several different amine/alkene combinations. Nonlinear...
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTExtrusion of Alkenes from Rhenium(V) Diolates: Energetics and MechanismKevin P. Gable Thuy N. PhanCite this: J. Am. Chem. Soc. 1994, 116, 3, 833–839Publication Date (Print):February 1, 1994Publication History Published online1 May 2002Published inissue 1 February 1994https://pubs.acs.org/doi/10.1021/ja00082a002https://doi.org/10.1021/ja00082a002research-articleACS PublicationsRequest reuse permissionsArticle Views386Altmetric-Citations90LEARN ABOUT...
Rates of cycloreversion phenyl-substituted diolates the type Cp*Re(O)(diolate), where diolate = phenylethane-1,2-diolate, exhibited a linear relationship with Hammett σ- constants, ρ 0.42. This suggests slight buildup electron density but little charge development in transition state. The better fit constants resonance interaction between phenyl ring and breaking C−O bond. On other hand, similar 1,2-diphenylethane-1,2-diolates showed curved behavior, acceleration by electron-donating...
Cycloreversion of 4-methoxystyrene from the corresponding Tp'Re(O)(diolato) complex (Tp' = hydrido-tris-(3,5-dimethylpyrazolyl)borate) was measured competitively for various isotopomers at 103 degrees C. Primary ((12)C/(13)C) and secondary ((1)H/(2)H) kinetic isotope effects were determined. The primary KIEs k(12C)/k(13C) 1.041 +/- 0.005 alpha position 1.013 0.006 beta position. Secondary k(H)/k(D) 1.076 1.017 Computational modeling (B3LYP/LACVP+) located a transition state concerted...
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTExtrusion of Alkenes from Rhenium(V) Diolates: The Effect Substitution and ConformationKevin P. Gable Jerrick J. JulietteCite this: Am. Chem. Soc. 1995, 117, 3, 955–962Publication Date (Print):January 1, 1995Publication History Published online1 May 2002Published inissue 1 January 1995https://pubs.acs.org/doi/10.1021/ja00108a012https://doi.org/10.1021/ja00108a012research-articleACS PublicationsRequest reuse permissionsArticle...
In situ reduction of Tp'ReO3 (Tp' = tris(3,5-dimethylpyrazolyl)hydridoborate) using triphenylphosphine or triethyl phosphite allows generation a reduced rhenium species that catalyzes efficient O atom transfer from epoxides to the stoichiometric phosphorus reductant at 75−105 °C. The reaction is stereospecific and proceeds most rapidly with cis- vs trans-alkenes. choice ligand shown impart advantages design catalytic cycle.
Hydridotris(3,5-dimethylpyrazolyl)boratorhenium(V) diolates cyclorevert to Tp'ReO3 and alkene at elevated temperatures in nonpolar solvents. Comparison of activation parameters those the analogous pentamethylcyclopentadienyl complexes show former have similar ΔS⧧'s, but higher ΔH⧧'s by 2−4 kcal/mol. Computation frontier orbitals for this ligand system that appropriate acceptor orbital on metal is pushed energy compared case where pentamethylcyclopentadienyl, consistent with predictions...
In the ocean surface layer and cell culture, polyamine transport protein PotD of SAR11 bacteria is often one most abundant proteins detected. Polyamines are organic cations at seawater pH produced by all living organisms thought to be an important component dissolved matter (DOM) in planktonic ecosystems. We hypothesized that cells uptake metabolize multiple polyamines use them as sources carbon nitrogen. Metabolic footprinting fingerprinting were used measure five compounds (putrescine,...
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTReversible oxidation of a strained alkene by Cp*ReO3Kevin P. Gable and Thuy N. PhanCite this: J. Am. Chem. Soc. 1993, 115, 7, 3036–3037Publication Date (Print):April 1, 1993Publication History Published online1 May 2002Published inissue 1 April 1993https://doi.org/10.1021/ja00060a086Request reuse permissionsArticle Views199Altmetric-Citations39LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum full text article downloads since...
Transfer of oxygen atoms from epoxides to triphenylphosphine is efficiently catalyzed by Tp′ReO3 [Tp′ = hydrido-tris-(3,5-dimethylpyrazolyl)borate] in benzene at 75-105 ºC. The reaction tolerates a wide variety functional groups including ketones (conjugated or non-conjugated the new double bond), esters, nitriles, ethers, silyl ethers and phthalimides. Relative rates vary with substitution pattern electronics; general, monosubstituted 2,2-disubstituted react fastest,...
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCatalytic and stoichiometric formation of cyclooctatetraenes from soluble nickel complexesChristophe J. Lawrie, Kevin P. Gable, Barry K. CarpenterCite this: Organometallics 1989, 8, 9, 2274–2276Publication Date (Print):September 1, 1989Publication History Published online1 May 2002Published inissue 1 September 1989https://pubs.acs.org/doi/10.1021/om00111a030https://doi.org/10.1021/om00111a030research-articleACS PublicationsRequest reuse...
Substituted 2-iodoaniline derivatives were prepared and utilized as reactants, along with asymmetric diarylacetylenes, to synthesize a series of 6-substituted-2,3-diarylindole via the Larock heteroannulation reaction. Electron-donating substituents on retarded reaction, while electron-withdrawing provided complete conversion indole products. In addition, electronic properties substituted reactants displayed no influence toward regioselectivity. On contrary, effect from unsymmetrical...
O atom transfer from epoxides cis-stilbene oxide and styrene to triphenylphosphine catalyzed by Tp'ReO(3) (Tp' = hydridotris(3,5-dimethylpyrazolyl)borate) is shown proceed via an unexpectedly complex combination of mechanisms. Reduction with PPh(3) in THF rapid above room temperature form a highly reactive species suggested be Tp'ReO(2). Spectroscopic examination attempts isolate this chromatography lead only Tp'Re(O)(OH)(2) (1); exposure the crude reduction mixture ethanol results formation...
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCondensation of Vicinal Diols with the Oxo Complex {Cp*Re(O)}2(.mu.-O)2 Giving Corresponding Diolate ComplexesKevin P. GableCite this: Organometallics 1994, 13, 6, 2486–2488Publication Date (Print):June 1, 1994Publication History Published online1 May 2002Published inissue 1 June 1994https://pubs.acs.org/doi/10.1021/om00018a048https://doi.org/10.1021/om00018a048research-articleACS PublicationsRequest reuse permissionsArticle...
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTFragmentation of, and Oxygen Atom Abstraction by, {CpRe(O)}2(.mu.-O)2Kevin P. Gable, Jerrick J. Juliette, Michael A. GartmanCite this: Organometallics 1995, 14, 7, 3138–3140Publication Date (Print):July 1, 1995Publication History Published online1 May 2002Published inissue 1 July 1995https://pubs.acs.org/doi/10.1021/om00007a007https://doi.org/10.1021/om00007a007research-articleACS PublicationsRequest reuse permissionsArticle...
The reaction enthalpy for O atom transfer from Cp*ReO3 to PPh3 in toluene solution is measured be −28.4 ± 0.3 kcal/mol and −28.0 0.6 THF solution. This allows the strength of ReO bond (in solution) estimated at 116.8 1.2 kcal/mol.
In situ reduction of Cp*ReO3 by PPh3 to form (Cp*ReO)2(µ-O)2 allows catalytic deoxygenation epoxides, however, conproportionation between the ReV and ReVII species clusters {(Cp*Re)3(µ-O)6}2+(ReO4–)2 new compound {(Cp*Re)3(µ2-O)3(µ3-O)3ReO3}+(ReO4–) leads removal rhenium from cycle loss activity.
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAcid-catalyzed trans to cis isomerization of [C5H5(CO)Fe]2(.mu.-CO)(.mu.-CH2)Charles P. Casey, Kevin Gable, and Dean M. RoddickCite this: Organometallics 1990, 9, 1, 221–226Publication Date (Print):January 1990Publication History Published online1 May 2002Published inissue 1 January 1990https://pubs.acs.org/doi/10.1021/om00115a034https://doi.org/10.1021/om00115a034research-articleACS PublicationsRequest reuse permissionsArticle...
Proposed mechanisms for the osmium-catalysed dihydroxylation are examined and kinetic rate laws derived in terms of various mechanistic constants. In light reported behaviour these systems, particularly with asymmetric nitrogen base ligands, several constraints can be placed on two major competing hypotheses. The chemical consequences make stepwise formation C–O bonds via an osmaoxetane more plausible model.
The ultraviolet–visible (UV-Vis) and Fourier transform infrared (FT-IR) spectroscopic studies carried out for the system UO 2 (NO 3 )/AHA/TBP (uranyl–acetohydroxamate–tributyl phosphate) confirmed presence of adduct )(AHA) ·2TBP with 1:1 stoichiometry :AHA (acetohydroxamic acid). spectrum this complex is identical to organic phase formed in uranium distribution experiments 30% TBP/n-dodecane AHA present aqueous phase. Disappearance hydroxyl stretching band a shift position carbonyl spectra...