3635-94-7Relevant academic research and scientific papers
Interaction of diazoalkanes with unsaturated compounds. 12. Stereochemistry of cyclopropanation of norbornenes with diazomethane in the presence of transition metal complexes
Dzhemilev, U. M.,Dokichev, V. A.,Maidanova, I. O.,Nefedov, O. M.,Tomilov, Yu. V.
, p. 697 - 700 (2007/10/02)
The stereochemistry of cyclopropanation of norbornenes with diazomethane in the presence of Cu, Pd, and Rh compounds has been studied.Stereoselectivity of the cyclopropanation depends on the nature of the transition metal and does not depend on its valent state or ligand environment.The reaction proceeds predominantly as exo-cycloaddition of the methylene fragment.The greatest amount of endo-isomer (up to 47 percent) is formed in cyclopropanation of norbornadiene and exo-tricyclo2,4>oct-6-ene in the presence of Cu and Rh compounds.
ORBITAL CONTROL OF STEREOCHEMISTRY IN ACID-CATALYSED ADDITION REACTIONS OF ENDO-TRICYCLO2.4>OCT-6-ENE
Battiste, Merle A.,Coxon, James M.,Simpson, Gregory W.,Steel, Peter J.
, p. 3137 - 3144 (2007/10/02)
The reaction of endo-tricyclo2.4>oct-6-ene 1 with methanol in the presence of catalytic amounts of toluene-p-sulphonic acid has been shown to give 2-exo- and endo-methoxybicyclooct-3-ene (2c) and (2d) and 2-endo-methoxybicyclooct-6-ene (13).The formation of 2-exo-methoxybicyclooct-3-ene (2c), the major product of reaction, has been probed by deuterium labelling experiments and a series of 6-exo-7-exo-dideuterobicyclooct-3-enes synthesised for (2)H, (1)H and (13)C NMR spectral analysis in order unambiguously to determine the stereochemistry of proton attack on endo-tricyclo2.4>oct-6-ene ( 1).The formation of 2-exo-methoxybicyclooct-3-ene (2c) has been determined to involve corner protonation of the cyclopropyl moiety and skeletal rearrangement to an allylic cation with a small but measurable memory effect.
