A5042129838- Cyclopropane Reaction Mechanisms
- Catalytic C–H Functionalization Methods
- Catalytic Alkyne Reactions
- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Synthetic Organic Chemistry Methods
- Asymmetric Synthesis and Catalysis
- Radiopharmaceutical Chemistry and Applications
- Boron Compounds in Chemistry
- Crystallography and molecular interactions
- Organoboron and organosilicon chemistry
Oregon State University
2021-2022
Regiodivergent transition metal-catalyzed B(4)- and C(1)-selenylation reactions of o -carboranes have been demonstrated.
A formal haloalkynylation of allenamides has been described for the synthesis highly stereo- and regioselective skipped halo enynes. Exclusive γ-regioselectivity is achieved through intermediacy a conjugated N-tosyliminium intermediate—direct evidence formation which was validated by NMR HRMS. Quantum mechanical computations reveal that reactive intermediate geometry key to controlling 1,2- or 1,4-regioselectivity alkyne interception. Divergent access elusive unsaturated systems also reported.
A mechanistic investigation into the origins of regio- and chemoselectivities observed in iron/pyridine dialdimine (PDAI)-catalyzed intermolecular [2+2+2] cycloaddition reactions terminal alkynes cyanamides to yield substituted 2-amino-pyridines is reported. The combination experimental computational studies disclosed herein reveals role hemilabile PDAI ligand as an important factor controlling resultant product's chemoselectivity.
This Claisen rearrangement establishes the feasibility of DyKAT γ-epimeric enals via dienamine formation to afford enantioenriched products. γ-Aryl and -alkyl enals, exocyclic that introduce quaternary centers, are all amenable substrates. Products readily converted into pyrrolidines or cyclopentenols. Notably, a reactive intermediate has been isolated from catalytic reaction, fully characterized, product upon reexposure reaction conditions. Product configuration arises directing C–H···π...