X-ray Crystal Structures and Conformational Analysis of Bicyclo[5.3.1]undec-1(11)-enes: Twisting versus Pyramidalization in Anti-Bredt Olefins

G.W. Wijsman, G.A. Iglesias, M.C. Beekman, W.H. De Wolf, F. Bickelhaupt, H. Kooijman, A.L. Spek

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

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.
Original languageEnglish
Pages (from-to)1216-1227
Number of pages11
JournalJournal of Organic Chemistry
Volume66
DOIs
Publication statusPublished - 2001

Fingerprint

Nucleophiles
Alkenes
Substitution reactions
Ethanol
Crystal structure
Derivatives
X rays
Water

Cite this

Wijsman, G. W., Iglesias, G. A., Beekman, M. C., De Wolf, W. H., Bickelhaupt, F., Kooijman, H., & Spek, A. L. (2001). X-ray Crystal Structures and Conformational Analysis of Bicyclo[5.3.1]undec-1(11)-enes: Twisting versus Pyramidalization in Anti-Bredt Olefins. Journal of Organic Chemistry, 66, 1216-1227. https://doi.org/10.1021/jo0013195
Wijsman, G.W. ; Iglesias, G.A. ; Beekman, M.C. ; De Wolf, W.H. ; Bickelhaupt, F. ; Kooijman, H. ; Spek, A.L. / X-ray Crystal Structures and Conformational Analysis of Bicyclo[5.3.1]undec-1(11)-enes: Twisting versus Pyramidalization in Anti-Bredt Olefins. In: Journal of Organic Chemistry. 2001 ; Vol. 66. pp. 1216-1227.
@article{3eafdd6e77df4d608d35b23f1843fb08,
title = "X-ray Crystal Structures and Conformational Analysis of Bicyclo[5.3.1]undec-1(11)-enes: Twisting versus Pyramidalization in Anti-Bredt Olefins",
abstract = "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.",
author = "G.W. Wijsman and G.A. Iglesias and M.C. Beekman and {De Wolf}, W.H. and F. Bickelhaupt and H. Kooijman and A.L. Spek",
year = "2001",
doi = "10.1021/jo0013195",
language = "English",
volume = "66",
pages = "1216--1227",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",

}

X-ray Crystal Structures and Conformational Analysis of Bicyclo[5.3.1]undec-1(11)-enes: Twisting versus Pyramidalization in Anti-Bredt Olefins. / Wijsman, G.W.; Iglesias, G.A.; Beekman, M.C.; De Wolf, W.H.; Bickelhaupt, F.; Kooijman, H.; Spek, A.L.

In: Journal of Organic Chemistry, Vol. 66, 2001, p. 1216-1227.

Research output: Contribution to JournalArticleAcademicpeer-review

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.

U2 - 10.1021/jo0013195

DO - 10.1021/jo0013195

M3 - Article

VL - 66

SP - 1216

EP - 1227

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

ER -