17152-77-1

Upstream product

• 498-66-8 norbornene 
• 108-95-2 phenol 
• 840-90-4 2-endo-norbornyl toluenesulfonate 
• 2534-77-2 exo-2-bromonorbornane 
• 139-02-6 sodium phenoxide 
• 498-66-8 norborn-2-ene 
• 540-38-5 p-Iodophenol 
• 109-99-9 tetrahydrofuran 
• 2628-16-2 p-acetoxystyrene 
• 77-73-6 bi(cyclopentadiene) 

Relevant academic research and scientific papers

NOVEL AROMATIC COMPOUNDS

The present invention comprises novel aromatic molecules, which can be used in the treatment of pathological conditions, such as cancer, skin diseases, muscle disorders, and immune system-related disorders such as disorders of the hematopoietic system including the hematologic system in human and veterinary medicine.

C(sp3)-C(sp2) cross-coupling of alkylsilicates with borylated aryl bromides-an iterative platform to alkylated aryl- and heteroaryl boronates

The attractive field of iterative cross-coupling has seen numerous advances, although almost exclusively in the union of sp2-hybridized partners. Conspicuously absent from this useful synthetic manifold is the inclusion of sp3-hybridized pronucleophiles that can undergo transmetalation under mild conditions. Described here is the use of primary and secondary ammonium alkylsilicates, which undergo facile C(sp3)-C(sp2) cross-coupling with borylated aryl bromide partners under photoredox/nickel dual catalysis conditions. This operationally simple procedure allows the production of alkylated small molecules possessing boronate ester (BPin, Bneopentyl, BMIDA) functional handles. Because of the extremely mild reaction conditions and the innocuous byproduct generated upon fragmentative oxidation of silicates, the corresponding borylated compounds were isolated in good to excellent yields. Aryl bromides bearing unprotected boronic acids are also generally tolerated for the first time and prove useful in multistep syntheses. Unlike many previously reported photoredox/Ni dual cross-couplings, the C(sp3)-C(sp2) bonds were forged using a transition metal-free photocatalyst, allowing a substantial increase in sustainability as well as a cost reduction. Because the developed Ni-catalyzed cross-coupling does not require discrete boron speciation control, as in many popular orthogonal Pd-based methods, this protocol represents a significant advance in atom- and step-economy.

Acid-Catalyzed Hydrolysis of Bridged Bi- and Tricyclic Compounds. XXVII. An Application of the Excess Acidity Method to the Norbornyl Cation Problem

Hydrolysis rates and products of exo- and endo-2-phenoxynorbornanes have been studied in concentrated aqueous perchloric acid solutions.The activation parameters, solvent deuterium isotope effects, dependences of the reation rates on acid concentration, products of hydrolysis and the high exo/endo rate ratio (2570) are all in agreement with the A-1 mechanism, in which the norbornyl cation is formed in the rate-limiting stage.The excess acidity method was used to determine first the pKa value (-5.56) and the slope parameter (m* = 1.01) for the oxygen protonation of the endo epimer, and then the slope parameters for the rate-limiting stages of the exo and endo hydrolyses (m* = 1.37 and 1.55, respectively).The slope parameters are somewhat exceptional, and may hint at a more delocalized charge in the transition state of the exo hydrolysis.

Palladium-catalyzed preparation of exo-aryl derivatives of the norbornane skeleton

Norbornene and norbornadiene derivatives have been shown to react with aryl and vinyl halides in the presence of a palladium catalyst, formic acid, and tributylamine or piperidine to give hydroarylated and hydrovinylated derivatives in good to high yield.Extension of the reaction to the hindered α,β-unsaturated aldehydic system of myrtenal produced a monocyclic derivative through a palladium-catalyzed ring opening.

REACTION OF exo-2-NORBORNYL AND 1-ADAMANTYL p-TOLUENESULFONATES WITH SODIUM PHENOXIDE IN TETRAHYDROFORAN. IONIZATION OF THE SUBSTRATES UNDER "APPARENTLY-SN2" CONDITIONS

exo-2-Norbornyl and 1-adamantyl tosylates react with sodium phenoxide in tetrahydrofuran via ionization, most probably through a cyclic transition state.The results call for attention in interpreting substitution reactions under "apperently-SN2" conditions.