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

doi:10.1021/jo0013195

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

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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 language	English
Pages (from-to)	1216-1227
Number of pages	11
Journal	Journal of Organic Chemistry
Volume	66
DOIs	https://doi.org/10.1021/jo0013195
Publication status	Published - 2001

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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",

}

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

SN - 0022-3263

VL - 66

SP - 1216

EP - 1227

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

ER -

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

Abstract

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