Vinylcyclopropane Rearrangement Research Articles

VINYLCYCLOPROPANE-CYCLOPENTENE REARRANGEMENT CATALYZED BY NICKEL(0) COMPLEXES

Abstract Bis(1,5-cyclooctadiene)nickel-tributylphosphine (1:1) catalyzed the vinylcyclopropane-cyclopentene rearrangement. Only such vinylcyclopropanes as those being capable of complexing with the catalyst (such as 1-substituted 1-cyclopropyl-1,3-butadienes and 1,1-dicyclopropylethylenes) were reactive.

Reaktionen Gespannter CC-einfachbindungen mit übergangsmetallen : XVIII. Zwischenstufen einer metallinduzierten vinylcyclopropan-cyclopenten-umlagerung in der 4,5-homotropiliden-reihe

The metal-induced vinylcyclopropane—cyclopentene rearrangement in the 4,5,-homotropilidene series involves successive cleavage of two bonds of the cyclopropane ring in the ligand sphere of a Fe 2(CO) 6 unit. The reaction has been studied by use of a reaction model in which the intermediates II, IV and V could be isolated and fully characterized. II and IV exhibit an interesting fluxional behavior.

ChemInform Abstract: THERMAL ISOMERIZATION OF (+)‐(1S,2S)‐TRANS,TRANS‐2‐METHYL‐1‐PROPENYLCYCLOPROPANE‐ QUANTIFICATION OF FOUR STEREOCHEMICAL PATHS IN A VINYLCYCLOPROPANE REARRANGEMENT

Chemischer InformationsdienstVolume 8, Issue 1 Preparative Organic Chemistry ChemInform Abstract: THERMAL ISOMERIZATION OF (+)-(1S,2S)-TRANS,TRANS-2-METHYL-1-PROPENYLCYCLOPROPANE- QUANTIFICATION OF FOUR STEREOCHEMICAL PATHS IN A VINYLCYCLOPROPANE REARRANGEMENT G. D. ANDREWS, G. D. ANDREWSSearch for more papers by this authorJ. E. BALDWIN, J. E. BALDWINSearch for more papers by this author G. D. ANDREWS, G. D. ANDREWSSearch for more papers by this authorJ. E. BALDWIN, J. E. BALDWINSearch for more papers by this author First published: January 4, 1977 https://doi.org/10.1002/chin.197701113Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume8, Issue1January 4, 1977 RelatedInformation

Photochemical 1,3-addition of methanol to t-butylbenzene

Irradiation of t-butylbenzene in methanol containing a trace of hydrochloric acid gives 4-methoxy-1-t-butyl-(1) and 6-methoxy-2-t-butyl-bicyclo[3.1.0]hex-2-ene (2a, b); the 4-methoxy-adduct is formed by addition of methanol to t-butylbenzvalene and the 6-methoxy-adducts may be formed by a sensitized vinylcyclopropane rearrangement, via a bicyclo[2.1.1]hexene intermediate, of the 4-methoxy-adduct.

Thermal isomerization of (+)-(1S,2S)-trans,trans-2-methyl-1-propenylcyclopropane: quantification of four stereochemical paths in a vinylcyclopropane rearrangement

Thermal isomerization of (+)-(1S,2S)-trans,trans-2-methyl-1-propenylcyclopropane: quantification of four stereochemical paths in a vinylcyclopropane rearrangement

Stereochemical specificity in the vinylcyclopropane rearrangement vs. MINDO/3 calculations

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTStereochemical specificity in the vinylcyclopropane rearrangement vs. MINDO/3 calculationsGerald D. Andrews and John E. BaldwinCite this: J. Am. Chem. Soc. 1976, 98, 21, 6706–6707Publication Date (Print):October 1, 1976Publication History Published online1 May 2002Published inissue 1 October 1976https://doi.org/10.1021/ja00437a051RIGHTS & PERMISSIONSArticle Views49Altmetric-Citations22LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (296 KB) Get e-Alerts Get e-Alerts

ChemInform Abstract: THERMAL REARRANGEMENT OF VINYLCYCLOPROPANES

Chemischer InformationsdienstVolume 7, Issue 37 Preparative Organic Chemistry ChemInform Abstract: THERMAL REARRANGEMENT OF VINYLCYCLOPROPANES E. M. MIL'VITSKAYA, E. M. MIL'VITSKAYASearch for more papers by this authorA. V. TARAKANOVA, A. V. TARAKANOVASearch for more papers by this authorA. F. PLATE, A. F. PLATESearch for more papers by this author E. M. MIL'VITSKAYA, E. M. MIL'VITSKAYASearch for more papers by this authorA. V. TARAKANOVA, A. V. TARAKANOVASearch for more papers by this authorA. F. PLATE, A. F. PLATESearch for more papers by this author First published: September 14, 1976 https://doi.org/10.1002/chin.197637100Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume7, Issue37September 14, 1976 RelatedInformation

Polar Substituents in Benzobarrelene Photochemistry; The Photoreactivities of Dimethyl 10‐methoxy‐ and Dimethyl 10,11‐dimethoxy‐2,3‐benzobicyclo[2.2.2]octateraene‐5,6‐dicarboxylate

AbstractThe direct irradiation of the monomethoxybarrelene 8 gives cyclooctatetraene product 18 (Φ = 0.075) via the anti‐Epiotis aromatic‐vinyldiester [2π+2π] bridging route, and two semibullvalenes 16 (Φ = 0.075) and 17 (Φ = 0.075) from di‐π‐methane rearrangements initiating from vinyl‐vinyldiester bridging. Benzophenone sensitization yields 16 (Φ =0.11) and 17 (Φ = 0.11). The dimethoxybarrelene 9 gives only semibullvalene 10, this resulting from di‐π‐methane rearrangement involving the vinyl and vinyldiester bridges, upon direct (Φ = 0.009) or benzophenone sensitized irradiations (Φ = 0.38). 10 undergoes a vinylcyclopropane rearrangement to give semibullvalene 11 upon direct or acetone sensitized irradiations (Φ = 0.008).

Regioselectivity and the role of olefin co-ordination in rhodium(I)-catalysed rearrangement of vinylcyclopropanes

Rearrangement of syn- and anti-7-vinylbicyclo-[4.1.0]heptanes in the presence of di-µ-chloro-tetra-carbonyldirhodium(I) exhibits kinetic behaviour and product selectivity which provide good evidence for initial co-ordination of the vinyl group and stereospecific cis-β-hydride elimination from a subsequent metallocyclic intermediate.

Structure and reactions of photothebainehydroquinone

The structure of photothebainehydroquinone, which was obtained by unsensitized irradiation with UV light of thebainequinone ( 1) or thebainehydroquinone ( 2) has been shown by X-ray crystallography to be 3a, which arises from 2 through a di-π-methane to vinylcyclopropane rearrangement. Treatment of 3a with acid gave 5a, 6a, 5b and probably 6b. Studies using DCl showed that the opening of the cyclopropane in 3a to give 5a, 5b, and 6a involved ‘end-on’ approach of the D +. The mechanisms of the reactions are discussed.

Stereospecific vinylcyclopropane rearrangement due to hindered rotation in the biradical

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTStereospecific vinylcyclopropane rearrangement due to hindered rotation in the biradicalJohn S. Swenton and Allan WexlerCite this: J. Am. Chem. Soc. 1971, 93, 12, 3066–3068Publication Date (Print):June 1, 1971Publication History Published online1 May 2002Published inissue 1 June 1971https://doi.org/10.1021/ja00741a053RIGHTS & PERMISSIONSArticle Views57Altmetric-Citations17LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (376 KB) Get e-Alerts Get e-Alerts

Conformational control of stereochemistry in the non-concerted, degenerate rearrangement of a vinylcyclopropane: (−)-Δ 3-Thujene

The stereochemistry of the degenerate, thermal vinylcyclopropane rearrangement of (−)-2,2,3-trideuterio-Δ 3-thujene has been elucidated. Determination of partitioning among the three products of enantiomerization and rearrangement to (+) and (−) 5,5,6-trideuterio-Δ 3-thujene reveals that the major path is forbidden by orbital symmetry and is therefore non-concerted, while the minor paths are equally divided between a forbidden and an allowed path. The high degree of stereoselectivity of this non-concerted rearrangement is explained by a small barrier to conformational equilibration. The rate of the racemization is given by the expression log k (sec −1) = 14·33–43·4/2·303 RT.

Mechanism of the vinylcyclopropane-cyclopentene rearrangement. Evidence against a concerted process

Mechanism of the vinylcyclopropane-cyclopentene rearrangement. Evidence against a concerted process

Structural evidence for the existence of a symmetrical high energy species in the degenerate vinylcyclopropane rearrangement

Structural evidence for the existence of a symmetrical high energy species in the degenerate vinylcyclopropane rearrangement

Recent Developments in the Stereochemistry of Cyclopropane Ring Opening

AbstractThis review article deals with the stereochemistry of the following ring opening reactions: 1. Homoallylic rearrangement of secondary and tertiary cyclopropyl alcohols in the presence of electrophilic reagents, 2. The addition of carboxylic acids to vinylcyclopropanes, 3. The thermal rearrangement of vinylcyclopropanes into cyclopentenes. An account is also given of the NMR spectroscopic determination of the conformations of substituted vinylcyclopropanes.

The pyrolysis of 3-vinyl-1-pyrazoline and 3-vinyl-1-pyrazoline-5,5-d2, and its relation to the vinylcyclopropane to cyclopentene rearrangement

The kinetics and products of the pyrolysis of 3-vinyl-1-pyrazoline (1) are described. The pyrolysis of 3-vinyl-1-pyrazoline-5,5-d2(II) produces vinylcyclopropane-2,2-d2and cyclopentene-4,4-d2. The secondary isotope effect has been measured (kH/kD = 1.21 ± 0.03), and the reaction mechanism is interpreted as proceeding through a nitrogen-free intermediate similar to that suggested for the rearrangement of vinylcyclopropane to cyclopentene. At 170° a dramatic change in the product composition occurs, and evidence is presented for a "hot vinylcyclopropane" being produced.

The Stereochemical Fate of the Cyclopropyl Ring in the Vinylcyclopropane Rearrangement

The Stereochemical Fate of the Cyclopropyl Ring in the Vinylcyclopropane Rearrangement