Dichlorocyclopropanation and ring cleavage of bridgehead enol lactones. A stereocontrolled ring expansion sequence

Shea, Kenneth J.; Fruscella, W. M.; England, W. P.

doi:10.1016/s0040-4039(00)96796-0

Cited by 14 publications

(4 citation statements)

References 20 publications

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“…The question becomes more intriguing when the cleavages of 165a and 165b are considered. 97 We recognize that possible intermediates 166a and 166b are type B bridgehead alkenes, as well as trans-cycloheptenones. A scattered variety of other trans-cyclononenoids have appeared.…”

Section: Bridgehead Double Bondsmentioning

confidence: 98%

“…Application of this 158 85 : 15 162 methodology also afforded 15995 and 160,96 the latter of which was converted to 162 via dichlorocyclopropanation, followed by ring cleavage. 97 It would certainly be interesting to know more about the conversion of 161 to 162. In particular, one might expect that the tetrahedral intermediate 163 would cleave according to path a, with direct formation of 162. However, dihalonorcaranes do not always follow the "normal" reactivity pattern; we showed98 that a process analogous to pathway b (to give 164) obtained in a dihalonorcarane solvolysis."…”

Section: Bridgehead Double Bondsmentioning

confidence: 99%

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Strained bridgehead double bonds

Warner¹

1989

Chem. Rev.

166

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Section: Bridgehead Double Bondsmentioning

confidence: 98%

Section: Bridgehead Double Bondsmentioning

confidence: 99%

Strained bridgehead double bonds

Warner¹

1989

Chem. Rev.

166

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“…An alternative strategy for the synthesis of medium‐sized rings by an addition–ring expansion strategy was developed for the stereospecific synthesis of substituted seven‐membered rings (Scheme ) 78. The exo addition of dichlorocarbene (PhHgCBrCl 2 , PhH, reflux) to bridgehead enol lactones 125 a′, 122 a′ , and 128 b′ produces bridgehead dichlorocyclopropanes 179, 181 , and 183 , respectively.…”

Section: Application Of the Type 2 Imda Reaction In Synthesesmentioning

confidence: 99%

The Type 2 Intramolecular Diels-Alder Reaction: Synthesis and Chemistry of Bridgehead Alkenes

Bear

Sparks

Shea

2001

Angew. Chem. Int. Ed.

188

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Anti‐Bredt alkenes, bicyclic molecules that contain a bridgehead double bond, were for many years regarded as chemical curiosities. The type 2 intramolecular Diels–Alder (IMDA) reaction provides a one‐step entry into this fascinating class of molecules. The reaction has made available numerous anti‐Bredt alkenes for structural and chemical studies. X‐ray crystallography has revealed the magnitude of the deformations associated with the bridgehead double bond, and rate studies of reactions of bridgehead alkenes have allowed quantification of the kinetic consequences of the torsional distortions. More recently, the type 2 intramolecular Diels–Alder reaction and the resulting anti‐Bredt alkenes have found application in organic synthesis. The constraints resulting from the connectivity in the Diels–Alder precursor creates a strong regio‐ and stereochemical bias in the cycloaddition step. The end result of this bias is the stereoselective synthesis of highly substituted six‐membered rings. The reaction also achieves a facile synthesis of seven‐ and eight‐membered rings in a single step from acyclic precursors. The utility of this reaction has been verified in recent applications of the type 2 IMDA reaction as a key step in the total synthesis of complex natural products.

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“…Eine alternative Strategie zur Synthese von Ringen mittlerer Größe durch Addition und Ringerweiterung wurde für die stereospezifische Synthese substituierter siebengliedriger Ringe entwickelt (Schema ) 78. Die exo ‐Addition von Dichlorcarben (PhHgCBrCl 2 , Benzol, Rückfluss) an die Brückenkopf‐Enollactone 125 a′, 122 a′ und 128 b′ führt zu den Brückenkopf‐Dichlorcyclopropanen 179, 181 bzw.…”

Section: Anwendungen Der Imda‐typ‐2‐reaktion In Der Syntheseunclassified

Intramolekulare Diels-Alder-Reaktion vom Typ 2: Synthese und Chemie von Brückenkopf-Alkenen

2001

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Sparks wurde 1972 geboren und wuchs in Stockbridge, Massachusetts, auf. Er erhielt seinen BSc 1995 am Rensselaer Polytechnic Institute, wobei er ein einjähriges Forschungspraktikum bei Burroughs Wellcome in der Abteilung für Organische Chemie absolvierte. Nach einem Jahr als Forschungslaborant bei Albany Molecular Research begann er seine Doktorarbeit an der UCI unter Anleitung von Professor Kenneth J. Shea. Zu seinen Forschungsinteressen gehört die Entwicklung von Hetero-Diels-Alder-Typ-2-Reaktionen und die Naturstoffsynthese. Kenneth J. Shea wurde in Queens im Staat New York geboren. Er erhielt den BSc und den MSc in Chemie von der University of Toledo. Seine Doktorarbeit führte er auf dem Gebiet der Physikalischen Organischen Chemie an der Pennsylvania State University durch. Nach einem Postdoc-Aufenthalt am California Institute of Technology wurde er 1974 Professor an der University of California in Irvine. Seine Forschungsinteressen sind auf präparative und mechanistische Organische Chemie, auf Polymerchemie und auf Materialforschung gerichtet. B. R. Bear K. J. Shea S. M. Sparks Schema 1. Vorschlag für eine Reaktionskaskade, die von 1 zu 3 führt.

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Dichlorocyclopropanation and ring cleavage of bridgehead enol lactones. A stereocontrolled ring expansion sequence

Cited by 14 publications

References 20 publications

Strained bridgehead double bonds

Strained bridgehead double bonds

The Type 2 Intramolecular Diels-Alder Reaction: Synthesis and Chemistry of Bridgehead Alkenes

Intramolekulare Diels-Alder-Reaktion vom Typ 2: Synthese und Chemie von Brückenkopf-Alkenen

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