TY - JOUR
T1 - Generation of the new quirogane skeleton by a vinylogous retro-Michael type rearrangement of longipinene derivatives
AU - Román, Luisa U.
AU - Rebeca Morales, N.
AU - Hernández, Juan D.
AU - Cerda-García-Rojas, Carlos M.
AU - Gerardo Zepeda, L.
AU - Flores-Sandoval, César A.
AU - Joseph-Nathan, Pedro
PY - 2001/8/20
Y1 - 2001/8/20
N2 - A new tricyclic hydrocarbon skeleton, named quirogane, was prepared by a vinylogous retro-Michael type molecular rearrangement of (4R,5S,7R,8R,9S,10R,11R)-7,8-diacetyloxy-9-mesyloxy-1-oxolongipin-2-ene (5). A remarkable difference in chemical behavior as compared to the corresponding 2,3-dihydroderivative of 5 is explained in terms of the stability of anionic intermediates, which were evaluated by AM1 calculations. The structure of the quirogane skeleton was confirmed by single crystal X-ray diffraction analysis of quirogadiene 6. A [2+2] photochemical cyclization of 6 afforded the highly strained pentacyclic sesquiterpenoid (10).
AB - A new tricyclic hydrocarbon skeleton, named quirogane, was prepared by a vinylogous retro-Michael type molecular rearrangement of (4R,5S,7R,8R,9S,10R,11R)-7,8-diacetyloxy-9-mesyloxy-1-oxolongipin-2-ene (5). A remarkable difference in chemical behavior as compared to the corresponding 2,3-dihydroderivative of 5 is explained in terms of the stability of anionic intermediates, which were evaluated by AM1 calculations. The structure of the quirogane skeleton was confirmed by single crystal X-ray diffraction analysis of quirogadiene 6. A [2+2] photochemical cyclization of 6 afforded the highly strained pentacyclic sesquiterpenoid (10).
KW - Cyclization
KW - Cyclobutanes
KW - Photochemistry
KW - Rearrangements
KW - Sesquiterpenes
UR - http://www.scopus.com/inward/record.url?scp=0035921107&partnerID=8YFLogxK
U2 - 10.1016/S0040-4020(01)00718-9
DO - 10.1016/S0040-4020(01)00718-9
M3 - Artículo
SN - 0040-4020
VL - 57
SP - 7269
EP - 7275
JO - Tetrahedron
JF - Tetrahedron
IS - 34
ER -