Synthesis and ring-opening metathesis of tetraalkoxy-substituted [2.2]paracyclophane-1,9-dienes

Chin Yang Yu; Madeleine Helliwell; James Raftery; Michael L. Turner

doi:10.1002/chem.201003147

Synthesis and ring-opening metathesis of tetraalkoxy-substituted [2.2]paracyclophane-1,9-dienes

Chin Yang Yu, Madeleine Helliwell, James Raftery, Michael L. Turner

Research output: Contribution to journal › Article › peer-review

Abstract

Tetraalkoxy-substituted [2.2]paracyclophane-1,9-dienes can be prepared in three steps from dithia- ACHTUNGTRENUNG[3.3]paracyclophanes. A mixture of pseudo-geminal and pseudo-ortho diastereomers is produced and the pure compounds can be separated by fractional crystallization. The solid state structures of these diastereomers reveal strongly distorted aromatic rings consistent with high levels of ring strain. Reaction of these diastereomers with the second generation Grubbs catalyst shows that only the pseudo-geminal isomer can be ring opened to give cis,trans-distrylbenzenes. The origin of this selectivity is discussed and the photoisomerization of the as-formed cis,- trans-product to the all trans isomer is demonstrated. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Original language	English
Pages (from-to)	6991-6997
Number of pages	6
Journal	Chemistry - A European Journal
Volume	17
Issue number	25
DOIs	https://doi.org/10.1002/chem.201003147
Publication status	Published - 14 Jun 2011

Keywords

cyclophanedienes
isomers
metathesis
phenylenevinylenes
strained molecules

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10.1002/chem.201003147

CCDC 755378: Experimental Crystal Structure Determination
Yu, C. Y. (Contributor), Helliwell, M. (Contributor), Raftery, J. (Contributor) & Turner, M. (Contributor), Cambridge Crystallographic Data Centre, 19 Nov 2009
DOI: 10.5517/cctc117, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cctc117&sid=DataCite
Dataset
CCDC 755377: Experimental Crystal Structure Determination
Yu, C. Y. (Contributor), Helliwell, M. (Contributor), Raftery, J. (Contributor) & Turner, M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2011
DOI: 10.5517/cctc106, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cctc106&sid=DataCite
Dataset
CCDC 755376: Experimental Crystal Structure Determination
Yu, C. Y. (Contributor), Helliwell, M. (Contributor), Raftery, J. (Contributor) & Turner, M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2009
DOI: 10.5517/cctc0z4, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cctc0z4&sid=DataCite
Dataset

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title = "Synthesis and ring-opening metathesis of tetraalkoxy-substituted [2.2]paracyclophane-1,9-dienes",

abstract = "Tetraalkoxy-substituted [2.2]paracyclophane-1,9-dienes can be prepared in three steps from dithia- ACHTUNGTRENUNG[3.3]paracyclophanes. A mixture of pseudo-geminal and pseudo-ortho diastereomers is produced and the pure compounds can be separated by fractional crystallization. The solid state structures of these diastereomers reveal strongly distorted aromatic rings consistent with high levels of ring strain. Reaction of these diastereomers with the second generation Grubbs catalyst shows that only the pseudo-geminal isomer can be ring opened to give cis,trans-distrylbenzenes. The origin of this selectivity is discussed and the photoisomerization of the as-formed cis,- trans-product to the all trans isomer is demonstrated. Copyright {\textcopyright} 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.",

keywords = "cyclophanedienes, isomers, metathesis, phenylenevinylenes, strained molecules",

author = "Yu, {Chin Yang} and Madeleine Helliwell and James Raftery and Turner, {Michael L.}",

note = "CAN 155:152226 25-29 Benzene, Its Derivatives, and Condensed Benzenoid Compounds School of Chemistry,The University of Manchester,Manchester,UK. Journal 1313496-52-4P Role: PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (crystal structure, failed ring-opening metathesis; prepn. and ring-opening metathesis of tetraalkoxy-substituted paracyclopanedienes); 1313496-49-9P; 1313496-51-3P; 1313496-87-5P Role: PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (crystal structure; prepn. and ring-opening metathesis of tetraalkoxy-substituted paracyclopanedienes); 246047-72-3 (Grubbs second generation catalyst) Role: CAT (Catalyst use), RCT (Reactant), USES (Uses), RACT (Reactant or reagent) (prepn. and ring-opening metathesis of tetraalkoxy-substituted paracyclopanedienes); 109-92-2 (Vinyl ethyl ether); 147274-72-4; 1313052-70-8 Role: RCT (Reactant), RACT (Reactant or reagent) (prepn. and ring-opening metathesis of tetraalkoxy-substituted paracyclopanedienes); 1313052-71-9P; 1313496-50-2P; 1313496-53-5P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and ring-opening metathesis of tetraalkoxy-substituted paracyclopanedienes); 1313052-72-0P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. and ring-opening metathesis of tetraalkoxy-substituted paracyclopanedienes)",

year = "2011",

month = jun,

day = "14",

doi = "10.1002/chem.201003147",

language = "English",

volume = "17",

pages = "6991--6997",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley & Sons Ltd",

number = "25",

}

TY - JOUR

T1 - Synthesis and ring-opening metathesis of tetraalkoxy-substituted [2.2]paracyclophane-1,9-dienes

AU - Yu, Chin Yang

AU - Helliwell, Madeleine

AU - Raftery, James

AU - Turner, Michael L.

N1 - CAN 155:152226 25-29 Benzene, Its Derivatives, and Condensed Benzenoid Compounds School of Chemistry,The University of Manchester,Manchester,UK. Journal 1313496-52-4P Role: PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (crystal structure, failed ring-opening metathesis; prepn. and ring-opening metathesis of tetraalkoxy-substituted paracyclopanedienes); 1313496-49-9P; 1313496-51-3P; 1313496-87-5P Role: PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (crystal structure; prepn. and ring-opening metathesis of tetraalkoxy-substituted paracyclopanedienes); 246047-72-3 (Grubbs second generation catalyst) Role: CAT (Catalyst use), RCT (Reactant), USES (Uses), RACT (Reactant or reagent) (prepn. and ring-opening metathesis of tetraalkoxy-substituted paracyclopanedienes); 109-92-2 (Vinyl ethyl ether); 147274-72-4; 1313052-70-8 Role: RCT (Reactant), RACT (Reactant or reagent) (prepn. and ring-opening metathesis of tetraalkoxy-substituted paracyclopanedienes); 1313052-71-9P; 1313496-50-2P; 1313496-53-5P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and ring-opening metathesis of tetraalkoxy-substituted paracyclopanedienes); 1313052-72-0P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. and ring-opening metathesis of tetraalkoxy-substituted paracyclopanedienes)

PY - 2011/6/14

Y1 - 2011/6/14

N2 - Tetraalkoxy-substituted [2.2]paracyclophane-1,9-dienes can be prepared in three steps from dithia- ACHTUNGTRENUNG[3.3]paracyclophanes. A mixture of pseudo-geminal and pseudo-ortho diastereomers is produced and the pure compounds can be separated by fractional crystallization. The solid state structures of these diastereomers reveal strongly distorted aromatic rings consistent with high levels of ring strain. Reaction of these diastereomers with the second generation Grubbs catalyst shows that only the pseudo-geminal isomer can be ring opened to give cis,trans-distrylbenzenes. The origin of this selectivity is discussed and the photoisomerization of the as-formed cis,- trans-product to the all trans isomer is demonstrated. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

AB - Tetraalkoxy-substituted [2.2]paracyclophane-1,9-dienes can be prepared in three steps from dithia- ACHTUNGTRENUNG[3.3]paracyclophanes. A mixture of pseudo-geminal and pseudo-ortho diastereomers is produced and the pure compounds can be separated by fractional crystallization. The solid state structures of these diastereomers reveal strongly distorted aromatic rings consistent with high levels of ring strain. Reaction of these diastereomers with the second generation Grubbs catalyst shows that only the pseudo-geminal isomer can be ring opened to give cis,trans-distrylbenzenes. The origin of this selectivity is discussed and the photoisomerization of the as-formed cis,- trans-product to the all trans isomer is demonstrated. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

KW - cyclophanedienes

KW - isomers

KW - metathesis

KW - phenylenevinylenes

KW - strained molecules

U2 - 10.1002/chem.201003147

DO - 10.1002/chem.201003147

M3 - Article

SN - 0947-6539

VL - 17

SP - 6991

EP - 6997

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 25

ER -

Synthesis and ring-opening metathesis of tetraalkoxy-substituted [2.2]paracyclophane-1,9-dienes

Abstract

Keywords

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Datasets

CCDC 755378: Experimental Crystal Structure Determination

CCDC 755377: Experimental Crystal Structure Determination

CCDC 755376: Experimental Crystal Structure Determination

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