Stereoselective synthesis of seven-membered carbocycles by a tandem cyclopropanation/Cope rearrangement between rhodium(II)-stabilized vinylcarbenoids and dienes

Davies, Huw M. L.; Clark, Tom; Smith, H. D.

doi:10.1021/jo00012a011

Cited by 107 publications

(52 citation statements)

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“…The diazo‐group transfer reaction from an appropriate azide onto a methylene group succeeds not only when the latter bears two strong acceptor substituents (acyl, cyano, nitro, sulfonyl, phosphoryl), but also for aryl‐,21, 28 heteroaryl‐,28 and vinylacetate substituents 29. The combination of p ‐acetamidobenzenesulfonyl azide and DBU has emerged as the method of choice for these applications.…”

Section: Synthesesmentioning

confidence: 99%

New Syntheses of Diazo Compounds

Maas

2009

Angew Chem Int Ed

243

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Diazo compounds (R1R2C=N2) are known as versatile and useful substrates for an array of chemical transformations and, therefore, diazo chemistry is still far from losing anything of its long-standing fascination. In addition to many studies on the subsequent chemistry of the diazo group, the inventory of methods for the preparation of diazo compounds is continuously supplemented by new methods and novel variations of established procedures. Several of these synthetic approaches take into account the lability and remarkable chemical reactivity of certain classes of diazo compounds, and environmentally more benign procedures also continue to be developed.

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Section: Synthesesmentioning

confidence: 99%

New Syntheses of Diazo Compounds

Maas

2009

Angew Chem Int Ed

243

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“…[29] Als Methode der Wahl hat sich hier die Kombination p-Acetamidobenzolsulfonylazid/DBU erwiesen. Für die Herstellung von a-Aryl-a-diazoketonen lässt sich die Kombination Sulfonylazid/DBU ebenfalls verwenden; in Abhängigkeit von der Art des Arylsubstituenten kann die Ausbeute jedoch stark vom verwendeten Azid, der Basenmenge und dem Solvens abhängen.…”

Section: Diazogruppenübertragung Auf Aktivierte Methylenverbindungenunclassified

“…Die Diazogruppenübertragung von geeigneten Aziden auf eine Methylengruppe gelingt nicht nur, wenn diese zwei starke Akzeptorsubstituenten (Acyl, Cyano, Nitro, Sulfonyl, Phosphoryl) trägt, sondern auch für Aryl-, [21,28] Hetaryl- [28] und Vinylessigester. [29] Als Methode der Wahl hat sich hier die Kombination p-Acetamidobenzolsulfonylazid/DBU erwiesen. Für die Herstellung von a-Aryl-a-diazoketonen lässt sich die Kombination Sulfonylazid/DBU ebenfalls verwenden; in Abhängigkeit von der Art des Arylsubstituenten kann die Ausbeute jedoch stark vom verwendeten Azid, der Basenmenge und dem Solvens abhängen.…”

Section: Diazogruppenübertragung Auf Aktivierte Methylenverbindungenunclassified

Neues zur Synthese von Diazoverbindungen

Maas

2009

Angewandte Chemie

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Aufgrund der vielseitigen und nützlichen Folgechemie von Diazoverbindungen (R1R2CN2) ist das Interesse an dieser Substanzklasse seit Jahren ungebrochen. Dabei wird auch das bereits vorhandene Methodenrepertoire zur Herstellung von Diazoverbindungen immer wieder um neue Verfahren oder um neuartige Varianten etablierter Synthesewege ergänzt. Nicht selten tragen die neuen Synthesevorschläge der Labilität und beachtlichen chemischen Reaktivität bestimmter Typen von Diazoverbindungen Rechnung, aber auch dem Aspekt umweltfreundlicherer Methodik wurde Beachtung geschenkt.

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“…Tandem methodology for heterocyclic synthesis represents a powerful approach for the rapid buildup of molecular complexity from potentially simple starting materials [10][11][12]. In the ongoing search for new domino processes in our laboratory, emphasis has been laid on sequential reactions which proceed cleanly and without forming by-products [13][14][15][16][17][18][19][20][21]. As a prerequisite for an ideally proceeding one-pot sequential transformation, the reactivity pattern of all participating components has to be such, that each building block gets involved in a reaction only when it is supposed to do so.…”

Section: Introductionmentioning

confidence: 99%

Tandem Methodology for Heterocyclic Synthesis

Padwa

2005

ChemInform

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Tandem methodology for heterocyclic synthesis represents a powerful approach for the rapid buildup of molecular complexity from potentially simple starting materials. Work from our laboratory has shown that the rhodium(II)-catalyzed cyclization cascade of α-diazo imides represents an effective method for the synthesis of a variety of heterocyclic systems. As an extension of these studies, we became interested in using a linked Pummerer/N-acyliminium ion cyclization sequence since we felt that this combination offers unique opportunities for the assemblage of complex target molecules. A synthetic method that combines transformations of different reaction types significantly broadens the scope of such procedures in synthetic chemistry. α-Thiocarbocations generated from the Pummerer reaction of β-phenylsulfinylmethyl-α,β-unsaturated amides can be intercepted by the adjacent amido group to produce transient amino-substituted furans which undergo subsequent Diels-Alder cycloadditions. Using this domino amido Pummerer/Diels-Alder cascade, we were able to assemble novel polycyclic systems in a single operation. The key step in the process involves the generation of a reactive N-acyliminium ion by fragmentation of an amino-substituted [4+2]-cycloadduct. The successful synthesis of a number of alkaloids by this sequence of reactions reveals the usefulness and importance of this unique domino cascade. Application of the process for the preparation of the stenoma alkaloid stenine was recently carried out in our laboratory.

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Stereoselective synthesis of seven-membered carbocycles by a tandem cyclopropanation/Cope rearrangement between rhodium(II)-stabilized vinylcarbenoids and dienes

Cited by 107 publications

References 0 publications

New Syntheses of Diazo Compounds

New Syntheses of Diazo Compounds

Neues zur Synthese von Diazoverbindungen

Tandem Methodology for Heterocyclic Synthesis

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