56684-97-0Relevant academic research and scientific papers
Rearrangement of (-)-β-caryophyllene. A product analysis and force field study
Fitjer, Lutz,Malich, Andreas,Paschke, Carola,Kluge, Sabine,Gerke, Ralf,Rissom, Beate,Weiser, J?rg,Noltemeyer, Mathias
, p. 9180 - 9189 (2007/10/03)
The rearrangement of (-)-β-caryophyllene (1) with sulfuric acid in ether has been reinvestigated. In the early stage, a multitude of products is formed. Of these, fourteen hydrocarbons (3, 4, 6-17) and four alcohols (5, 18-20) were obtained pure. From the very beginning, the tricycloundecenes 15-17 assumulate quickly. This indicates that a previously unknown rearrangement of 1 by protonation of the exocyclic double bond followed by transannular ring closure is a main reaction, and that the conformation βα is involved. Three hydrocarbons (3, 4, 8) and three alcohols (5, 18, 19) proved to be stable. They are the main components in the late stage. A complete rearrangement scheme followed from a force field analysis using MMP2. First, all conformations up to 4 kcal above the global minimum of each product and each carbenium ion necessary for its formation were detected automatically using the search program HUNTER. Second, the conformation favoring a specific transformation was searched for. For transannular cyclizations, the conformation with the shortest distance between the atoms to be bound and, for ring openings and 1,2-shifts, the conformation with the smallest dihedral angle between the empty p-orbital and the bond to be broken were selected. In all cases, the selection criteria proved valid: The stereochemistry of the conformations selected matched the stereochemistry of the products observed. On the basis of the results presented, a fully automated search program for favorable rearrangement paths may be developed.
MERCURATION OF CARYOPHYLLENE OXIDE IN ACETIC ACID. CONFORMATIONS OF β-PANASINSENE, β-PANASINSEN-5α-OL, AND β-PANASINSEN-5-ONE
Tkachev, A. V.,Mamatyuk, V. I.,Dubovenko, Zh. V.
, p. 475 - 481 (2007/10/02)
The structure of β-panasinsen-5α-ol, i.e., the main product from the mercuration of caryophyllene 4β,5α-epoxide in acetic acid, was studied.The conformations in solutions of β-panasinsen-5α-ol and related compounds (β-panasinsene and β-panasinsen-5-one) were determined on the basis of the data from the 1H and 13C NMR spectra.A scheme is proposed for the formation of β-panasinsen-5α-ol in the reaction of caryophyllene 4β,5α-epoxide with mercuric acetate.
STEREOHCEMICALLY ABNORMAL CYCLIZATION OF CARYOPHYLLENE BY THE ACTION OF MERCURY(II) ACETATE
Tkachev, A. V.,Gatilov, Yu. V.,Bagryanskaya, I. Yu.,Shakirov, M. M.,Mamatyuk, V. I.,et al.
, p. 490 - 503 (2007/10/02)
The products from mercuration-demercuration of the sesquiterpene hydrocarbon caryophyllene by the action of mercury(II) acetate in acetic acid were studied.The chemical structure of the main reaction product 1,4,4-trimethyltricyclo2.5>dodec-8-ene was determined by 13C NMR on the basis of an analysis of the spin-spin coupling constants 1J (13C-13C).The stereochemical structure was established by x-ray crystallographic analysis of the corresponding epoxide.A mechanism is proposed for the isomerization of caryophyllene into compounds with the tricyclo2,5>dodecane skeleton, including intramolecular attack by the mercury-containing function at the C=C bond.It was established that biomimetic cyclization of caryophyllene to β-panasinsene occurs with mercury(II) acetate in acetic acid (followed by reductive demercuration).
TOTAL SYNTHESIS OF α- AND β-PANASINSENE
McMurry, John E.,Choy, William
, p. 2477 - 2480 (2007/10/02)
α- and β-panasinsene have been synthesized by a route which employs intramolecular cuprous triflate catalyzed photocyclization of an olefin with an allylic alcohol.
