TY - JOUR
T1 - X-ray Crystal Structures and Conformational Analysis of Bicyclo[5.3.1]undec-1(11)-enes: Twisting versus Pyramidalization in Anti-Bredt Olefins
AU - Wijsman, G.W.
AU - Iglesias, G.A.
AU - Beekman, M.C.
AU - De Wolf, W.H.
AU - Bickelhaupt, F.
AU - Kooijman, H.
AU - Spek, A.L.
PY - 2001
Y1 - 2001
N2 - The synthesis of several 9,11,11-trihalo[5.3.1]propellanes and their 4-dimethylsila analogues is described. They solvolyze under formation of the corresponding isomeric 7,9,11- trihalobicyclo-[5.3.1]undec-1(11)-enes which are "anti-Bredt" olefins with a strained trans double bond in a bridged eight-membered ring; in the presence of nucleophiles such as water or ethanol, the corresponding 7-hydroxy or 7-ethoxy derivatives, respectively, are obtained. On the basis of the X-ray crystal structures of four of these compounds (1a, 9a, 15, 17b), the effect of strain and of the substitution pattern on the degree of twisting and pyramidalization of the double bond is discussed.
AB - The synthesis of several 9,11,11-trihalo[5.3.1]propellanes and their 4-dimethylsila analogues is described. They solvolyze under formation of the corresponding isomeric 7,9,11- trihalobicyclo-[5.3.1]undec-1(11)-enes which are "anti-Bredt" olefins with a strained trans double bond in a bridged eight-membered ring; in the presence of nucleophiles such as water or ethanol, the corresponding 7-hydroxy or 7-ethoxy derivatives, respectively, are obtained. On the basis of the X-ray crystal structures of four of these compounds (1a, 9a, 15, 17b), the effect of strain and of the substitution pattern on the degree of twisting and pyramidalization of the double bond is discussed.
UR - https://www.scopus.com/pages/publications/0035936778
UR - https://www.scopus.com/inward/citedby.url?scp=0035936778&partnerID=8YFLogxK
U2 - 10.1021/jo0013195
DO - 10.1021/jo0013195
M3 - Article
SN - 0022-3263
VL - 66
SP - 1216
EP - 1227
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
ER -
