66966-40-3

Upstream product

• 67010-34-8 endo-3-phenyl-exo-tricyclo<3.2.1.0^2,4>octane 
• 498-66-8 norborn-2-ene 
• 100-44-7 benzyl chloride 
• 908094-04-2 phenyldiazomethane 
• 100-51-6 benzyl alcohol 
• 498-66-8 norbornene 
• 100-39-0 benzyl bromide 
• 100-52-7 benzaldehyde 

Downstream Products

• 74998-81-5 Acetic acid (S)-(1R,2R,4S)-bicyclo[2.2.1]hept-2-yl-phenyl-methyl ester 
• 74998-80-4 Acetic acid (R)-(1R,2R,4S)-bicyclo[2.2.1]hept-2-yl-phenyl-methyl ester 
• 67683-47-0 (1S,4R)-2-[1-Phenyl-meth-(E)-ylidene]-bicyclo[2.2.1]heptane 
• 67683-48-1 (1R,4S)-2-[1-Phenyl-meth-(E)-ylidene]-bicyclo[2.2.1]heptane 

Relevant academic research and scientific papers

COMPETITIVE PROCESSES IN PALLADIUM-CATALYZED C-C BOND FORMATION

A palladium-carbon bond, stable towards hydrogen elimination, undergoes various insertion and reductive elimination reactions, depending on availability of facile reductive elimination steps.

Palladium(0)-catalyzed cyclopropanation of benzyl bromides via C(sp 3)-H bond activation

A novel and highly efficient Pd(0)-catalyzed domino reaction to prepare cyclopropane derivatives has been established. The process involves a Heck-type coupling reaction and a C(sp3)-H bond activation. Preliminary DFT calculations suggest that a four-membered palladacycle intermediate is involved. This journal is the Partner Organisations 2014.

Unconjugated Arylcyclopropanes. Acid-Catalyzed Addition of Acetic Acid to Highly Hindered Arylcyclopropanes

The adduct of 1-naphthylcarbene and norbornene, endo-3-(1-naphthyl)-exo-tricyclo2,4>octane (9) has been prepared. 1H and 13C NMR spectra of this system indicate that the unconjugated arylcyclopropane conformation is favored.Rotation about the naphthyl-cyclopropane bond is restricted.The temperature-dependent NMR indicates a 16.9 kcal/mol barrier to attainment of the conjugated conformation.Acetic acid adds readily under acid catalysis to the phenyl analogue exo-3-phenyl-exo-tricyclo2,4>octane (3) and more slowly to the more strained endo-3-phenyl-exo-tricyclo2,4>octane (4).Kinetic data suggest the involvement of a cationic intermediate with little transition-state charge development at the benzylic carbon.The rates of addition to substituted analogues of 3 and 4 correlate with Hammett ? values, giving ρ values of 2.53 and 2.35, respectively.Product-analysis data support the involvement of a benzylic cation, 23.The slower rate of reaction of the more strained endo isomers has been interpreted in terms of a barrier to attainment of the conjugated conformation which appears to be the favorable conformation for protonation of arylcyclopropanes.This suggestion is supported by the observation that the unconjugated systems, exo- and endo-3-(2,6-dimethylphenyl)-exo-tricyclo-2,4>octanes (27 and 28), add acetic acid 480 and 6.2 x 104 times, respectively, more slowly than 3.