Recent Developments in Fulvene and Heterofulvene Chemistry

Kawase, Takeshi; Kurata, Hiroyuki

doi:10.1002/9783527671182.ch6

Cited by 10 publications

(11 citation statements)

References 400 publications

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“…The exocyclic double bond of fulvenes is easily polarised, giving rise to dipolar resonance structures (Scheme 1) [1–3 5,9,31–32 40–48].…”

Section: Reviewmentioning

confidence: 99%

“…In addition, fulvenes readily participate in cycloaddition reactions, which will be discussed in more detail in successive sections. The high reactivity of fulvenes is mostly centred about the polarisable exocyclic double bond [1–3 5–6 9,14,32,40,42–45 48,56,61–67]. By considering the dipolar resonance structures of fulvenes, whereby either cationic ( 1a and 2a ) or anionic ( 1b and 2b ) charged centres are formed at the cyclic carbon of the exocyclic double bond, their aromatic character and reactivity becomes more predictable [1–2 5,9,30,42–45 48,52–54 56,62–64 67–69] (Scheme 1).…”

Section: Reviewmentioning

confidence: 99%

“…Reactions of (a) 6,6-dimethylpentafulvene participating as 2π and 4π components in cycloadditions with p -benzoquinone to afford [2 + 3] ( 7 ) and [4 + 2] ( 8 ) cycloadducts, and (b) 6-(dimethylamino)pentafulvene participating as a 6π component in a [6 + 3] cycloaddition with p -benzoquinone to afford cycloadduct 9 [32]. …”

Section: Reviewmentioning

confidence: 99%

“…1). Historically, fulvenes were of great interest as a result of their unique reactivity resulting from their exocyclic double bond [9,29–32], and more recently, as intermediates in the synthesis of more complex polycyclic scaffolds via cycloaddition reactions. While this highlight article will focus primarily on the cycloaddition chemistry of fulvenes and its applications, a brief introduction to the properties and reactivity of fulvenes, important to understanding their participation in cycloaddition reactions, is initially provided.…”

Section: Introductionmentioning

confidence: 99%

“…2). The introduction of heteroatoms results in differing reactivities, which can be further influenced by substituents, making them useful building blocks for the synthesis of polycyclic compounds [32,35–39]. This is another rich and interesting area of chemistry, although further discussion of heterofulvenes is outside the scope of the current overview and the reader is directed to a very good review by Kawase and Kurata [32].…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

An overview of the cycloaddition chemistry of fulvenes and emerging applications

Swan¹,

Platts²,

Blencowe³

2019

Beilstein J. Org. Chem.

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The unusual electronic properties and unique reactivity of fulvenes have interested researchers for over a century. The propensity to form dipolar structures at relatively low temperatures and to participate as various components in cycloaddition reactions, often highly selectively, makes them ideal for the synthesis of complex polycyclic carbon scaffolds. As a result, fulvene cycloaddition chemistry has been employed extensively for the synthesis of natural products. More recently, fulvene cycloaddition chemistry has also found application to other areas including materials chemistry and dynamic combinatorial chemistry. This highlight article discusses the unusual properties of fulvenes and their varied cycloaddition chemistry, focussing on applications in organic and natural synthesis, dynamic combinatorial chemistry and materials chemistry, including dynamers, hydrogels and charge transfer complexes. Tables providing comprehensive directories of fulvene cycloaddition chemistry are provided, including fulvene intramolecular and intermolecular cycloadditions complete with reactant partners and their resulting cyclic adducts, which provide a useful reference source for synthetic chemists working with fulvenes and complex polycyclic scaffolds.

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“…The exocyclic double bond of fulvenes is easily polarised, giving rise to dipolar resonance structures (Scheme 1) [1–3 5,9,31–32 40–48].…”

Section: Reviewmentioning

confidence: 99%

Section: Reviewmentioning

confidence: 99%

Section: Reviewmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

An overview of the cycloaddition chemistry of fulvenes and emerging applications

Swan¹,

Platts²,

Blencowe³

2019

Beilstein J. Org. Chem.

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Ein Boratafulven

2021

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Borole mit Bor‐gebundenen Alkylresten wurden hergestellt und charakterisiert und die Auswirkungen von Alkylsubstituenten auf die elektronischen Eigenschaften untersucht. Die Deprotonierung einer exozyklischen, Bor‐gebundenen Methylgruppe in einem B‐Methylborol führt zum 5‐Boratafulvenanion – einem Isomer des Boratabenzols. Das Boratafulven wurde charakterisiert, und die elektronischen Eigenschaften wurden durch DFT‐Rechnung untersucht. Eine computerchemische Abschätzung der pKs‐Werte der exozyklischen B‐CH3‐Gruppen für Substitutionsderivate des Borols weist auf eine erhöhte C‐H‐Azidität infolge des in einen antiaromatischen Ring eingebetteten Boratoms hin. Das nicht‐aromatische Boratafulven reagiert als C‐zentriertes Nukleophil mit dem milden Elektrophil Me3SnCl, unter Zurückgewinnung des antiaromatischen Charakters, zu einem Stannylmethylborol. Als nukleophile Synthone für Borole eröffnen Boratafulvene einen neuen Zugang zu diesen hochreaktiven Heterozyklen. Das Boratafulven reagiert gegenüber Benzophenon als Methylen‐Transferreagenz in einer bora‐Wittig‐artigen Reaktion unter Bildung eines Boroloxids.

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A Boratafulvene

2021

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Structurally authenticated free B-alkylb oroles are presented and electronic implications of alkylsubstitution were assessed. Deprotonation of ab oron-bound exocyclic methyl group in aB -methyl borole yields the first 5-boratafulvene anion-an isomer to boratabenzene.Boratafulvene was structurally characterized and its electronic structure probed by DFT calculations.T he pK a value of the exocyclic B À CH 3 in as et of boroles was computationally approximated and confirmed apronounced acidic character caused by the boron atom embedded in an anti-aromatic moiety.The non-aromatic boratafulvene reacts as aC-centered nucleophile with the mild electrophile Me 3 SnCl to give as tannylmethyl borole,r egenerating the anti-aromaticity.A sn ucleophilic synthons for boroles,b oratafulvenes thus open an entirely new avenue for synthetic strategies towardt his highly reactive class of heterocycles.Boratafulvene reacts as amethylene transfer reagent in abora-Wittig-type reaction generating aborole oxide.

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Recent Developments in Fulvene and Heterofulvene Chemistry

Cited by 10 publications

References 400 publications

An overview of the cycloaddition chemistry of fulvenes and emerging applications

An overview of the cycloaddition chemistry of fulvenes and emerging applications

Ein Boratafulven

A Boratafulvene

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