A5039738361- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Asymmetric Hydrogenation and Catalysis
- Catalytic C–H Functionalization Methods
- Organometallic Complex Synthesis and Catalysis
- Synthesis and Catalytic Reactions
- Catalytic Cross-Coupling Reactions
- Carbon dioxide utilization in catalysis
- CO2 Reduction Techniques and Catalysts
- Oxidative Organic Chemistry Reactions
- Synthetic Organic Chemistry Methods
- Catalytic Processes in Materials Science
- Nanomaterials for catalytic reactions
- Alkaloids: synthesis and pharmacology
Bristol-Myers Squibb (United States)
2024
University of California, Berkeley
2020-2023
Lawrence Berkeley National Laboratory
2022-2023
Carleton College
2017-2020
ConspectusCatalytic intermolecular hydroamination of alkenes is an atom- and step-economical method for the synthesis amines, which have important applications as pharmaceuticals, agrochemicals, catalysts, materials. However, hydroaminations in high yield with selectivity are challenging to achieve because these reactions often lack a thermodynamic driving force accompanied by side reactions, such alkene isomerization, telomerization, oxidative amination. Consequently, early examples were...
Remote hydrofunctionalizations of alkenes incorporate functional groups distal to existing carbon–carbon double bonds. While remote carbonylations are well-known, most common for addition relatively nonpolar B–H, Si–H, and C–H bonds with alkenes. We report a system the hydroamination disubstituted functionalize an alkyl chain selectively at subterminal, unactivated, methylene position. Critical high regioselectivity reaction rates electronic properties substituent on amine development ligand...
The synthesis and characterization of base-stabilized base-free pincer-type bis(phosphine)/silylene [P<sub>2</sub>Si]Ru complexes are reported. complex performs cooperative, silylene-assisted hydride transfer to CO<sub>2</sub> CS<sub>2</sub>.
Hydroamination of alkenes catalyzed by transition-metal complexes is an atom-economical method for the synthesis amines, but reactions unactivated remain inefficient. Additions N–H bonds to such iridium, gold, and lanthanide catalysts are known, they have required a large excess alkene. New mechanisms processes involving metals rarely used previously hydroamination could enable these occur with greater efficiency. We report ruthenium-catalyzed intermolecular hydroaminations variety terminal...
Pd(COD)(DQ) (COD=1,5-cyclooctadiene, DQ=duroquinone) is a robust, air-stable, and well-defined 18-electron Pd(0)–olefin complex first synthesized by Sakai et al. in 1983. Herein, we describe an operationally convenient synthetic procedure to prepare this on decagram scale; show that it undergoes facile ligand exchange with phosphines, N-heterocyclic carbenes, other catalytically important ancillary ligands give stable organometallic products; demonstrate its catalytic competence numerous...
Abstract A metal/ligand cooperative approach to the reduction of small molecules by metal silylene complexes (R 2 Si=M) is demonstrated, whereby silicon activates incoming substrate and mediates net two‐electron transformations one‐electron redox processes at two centers. An appropriately tuned cationic pincer cobalt(I) complex, featuring a central donor, reacts with CO afford bimetallic siloxane, Co II centers, liberation CO; reaction complex ethylene yields similar product an bridge....
The use of carboxylate bases with low solubility in organic solvents often poses a challenge the large-scale application palladium-catalyzed Miyaura borylation aryl halides due to variability kinetic behavior reaction stemming from scale-dependent mass-transfer effects. Herein, we report that combination potassium pivalate (KOPiv, base improved solvents) and 2-PrOH cosolvent obviates challenges associated performing insoluble on scale. This solubility-driven protocol improves both physical...
Recent studies in transition metal catalysis employing chelating phosphines have suggested a role for partial ligand oxidation formation of the catalytically active species, with potentially widespread relevance number catalytic systems. We examine internal redox reaction PdII(bisphosphine)X2 (X = Cl, OAc, etc.) complexes to reveal previously underexplored aspects bisphosphine monoxides (BPMOs), including evaluation structure and development general conditions access collection structurally...
Recent studies in transition metal catalysis employing chelating phosphines have suggested a role for partial ligand oxidation formation of the catalytically active species, with potentially widespread relevance number cata-lytic systems. We examine internal redox reaction PdII(bisphosphine)X2 (X = Cl, OAc, etc.) complexes to reveal previously underexplored aspects bisphosphine mono-oxides (BPMOs), including evaluation structure and development general conditions access collection...
Abstract A metal/ligand cooperative approach to the reduction of small molecules by metal silylene complexes (R 2 Si=M) is demonstrated, whereby silicon activates incoming substrate and mediates net two‐electron transformations one‐electron redox processes at two centers. An appropriately tuned cationic pincer cobalt(I) complex, featuring a central donor, reacts with CO afford bimetallic siloxane, Co II centers, liberation CO; reaction complex ethylene yields similar product an bridge....
Asymmetric alkene hydroamination could be a direct route to valuable chiral amines from abundant feedstocks. However, most asymmetric hydroaminations have limited value because they require large excess of alkene, occur with modest enantioselectivity, and tolerance functional groups. We report an enantioselective, intermolecular unactivated terminal alkenes that occurs equimolar amounts amine, tolerates many groups, in high yield, enantioselectivity turnover numbers. Mechanistic studies...