Perylene Synthesis by the Parallel Cycloaromatization of Adjacent Enediynes

Chow, S.-Y.; Palmer, Grant J.; Bowles, Daniel M.; Anthony, John E.

doi:10.1021/ol005615f

Cited by 18 publications

(10 citation statements)

References 21 publications

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“…Binaphthyl 202 was likewise obtained as a minor product in 10% yield (Scheme 52). 189 Interestingly, when the same process was carried out on bulky derivatives (R 1 = tBu), the cycloaromatization took place exclusively on the unsubstituted enediyne core, and naphthalene 203 was obtained in 20% yield along with a large amount of by-products (Scheme 52). 189…”

Section: Scheme 37mentioning

confidence: 99%

(Hetero)aromatics from dienynes, enediynes and enyne–allenes

et al. 2016

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The construction of aromatic rings has become a key objective for organic chemists. While several strategies have been developed for the functionalization of pre-formed aromatic rings, the direct construction of an aromatic core starting from polyunsaturated systems is yet a less explored field. The potential of such reactions in the formation of aromatics increased at a regular pace in the last few years. Nowadays, there are reliable and well-established procedures to prepare polyenic derivatives, such as dienynes, enediynes, enyne-allenes and hetero-analogues. This has stimulated their use in the development of innovative cycloaromatizations. Different examples have recently emerged, suggesting large potential of this strategy in the preparation of (hetero)aromatics. Accordingly, this review highlights the recent advancements in this field and describes the different conditions exploited to trigger the process, including thermal and photochemical activation, as well as the use of transition metal catalysis and the addition of electrophiles/nucleophiles or radical species.

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Section: Scheme 37mentioning

confidence: 99%

(Hetero)aromatics from dienynes, enediynes and enyne–allenes

et al. 2016

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“…4,5 The Diels-Alder and cyclotrimerisation reactions 3 (orange), belonging to the pool of cycloaddition reactions, together with the Bergman cyclisation reaction [11][12][13] (red) represent the main tools for the construction of benzenoid cutouts of graphene, such as polycyclic aromatic hydrocarbons (PAHs). 14 …”

Section: Acetylene As a Unique Synthetic Toolmentioning

confidence: 99%

“…Conjugation-related representative examples of triazole-derived oligomeric(8)(9)(10)(11)(12)(13)(14) and polymeric(15)(16)(17)(18)(19)(20)(21) structures as potential materials for organic optoelectronics.…”

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confidence: 99%

Triazole: a unique building block for the construction of functional materials

2011

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Over the past 50 years, numerous roads towards carbon-based materials have been explored, all of them being paved using mainly one functional group as the brick: acetylene. The acetylene group, or the carbon-carbon triple bond, is one of the oldest and simplest functional groups in chemistry, and although not present in any of the naturally occurring carbon allotropes, it is an essential tool to access their synthetic carbon-rich family. In general, two strategies towards the synthesis of π-conjugated carbon-rich structures can be employed: (a) either the acetylene group serves as a building block to access acetylene-derived structures or (b) it serves as a synthetic tool to provide other, usually benzenoid, structures. The recently discovered copper-catalysed azide-alkyne cycloaddition (CuAAC) reaction, however, represents a new powerful alternative: it transforms the acetylene group into a five-membered heteroaromatic 1H-1,2,3-triazole (triazole) ring and this gives rise to new opportunities. Compared with all-carbon aromatic non-functional rings, the triazole ring possesses three nitrogen atoms and, thus, can serve as a ligand to coordinate metals, or as a hydrogen bond acceptor and donor. This Feature Article summarises examples of using the triazole ring to construct conjugation- and/or function-related heteroaromatic materials, such as tuneable multichromophoric covalent ensembles, macrocyclic receptors or responsive foldamers. These recent examples, which open a new sub-field within organic materials, started to appear only few years ago and represent "a few more bricks" on the road to carbon-rich functional materials.

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“…Aryl-bound functional groups which are tolerated in Pd-mediated arylations include ortho-alkynyl [63], ortho-vinyl [64], ortho-nitro [65], and ortho-formyl groups [66]. Some examples of Pd-mediated cross-coupling reactions are depicted in Schemes 8.4 and 8.5, to illustrate the required conditions and scope of these reactions.…”

Section: Cross-couplingmentioning

confidence: 99%

Palladium‐Catalyzed CC Bond Formation

Dörwald

2004

Side Reactions in Organic Synthesis

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The development in recent decades of numerous different Pd-catalyzed C-C bondforming reactions has had a huge impact on synthetic organic chemistry [1][2][3][4][5][6][7][8][9][10]. Several classes of compounds, for example unsymmetrical biaryls or substituted polyenes, which were difficult if not impossible to synthesize in the 1950s, can now be readily prepared under mild conditions with high regio-and stereoselectivity via Pdcatalyzed cross-coupling reactions. The compatibility of Pd-catalysis with many functional groups and protic solvents, together with its broad scope, has secured a central role for this chemistry in organic synthesis.The most important Pd-catalyzed C-C bond-forming reactions proceed according to the mechanisms outlined in Schemes 8.3 and 8.6. In these reactions a Pd(0) complex, which can be generated in situ by reduction of Pd(II), undergoes oxidative addition to an organic halide or sulfonate to yield an organopalladium(II) complex. This reaction is rapid with aryl or vinyl halides but proceeds more slowly with alkyl halides [9]. The reactivity decreases in the order RI > ROTf » RBr >> RCl >> RF [11], and electron-poor aryl or vinyl halides react with Pd(0) complexes faster than electron-rich halides. The resulting organopalladium(II) complex can react with alkenes or a variety of organometallic compounds, forming the C-C bond and regenerating the catalytically active Pd(0) complex. Chemical Properties of Organopalladium CompoundsThe synthetically most important Pd-catalyzed C-C bond-forming reactions proceed via intermediate square planar organopalladium(II) complexes of the type PdRL 3 , in which the ligands L are usually halide or phosphine ligands. Organopalladium(II) complexes are rather stable organometallic compounds which can be readily prepared and isolated [12][13][14]. Complexes such as PdArL 2 X with L representing phosphines or amines and X being a halogen do not usually react with water, and Pd-mediated C-C bond-forming reactions can be conducted in the presence of water 8 Palladium-catalyzed C-C Bond Formation Side Reactions in Organic Synthesis.

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Perylene Synthesis by the Parallel Cycloaromatization of Adjacent Enediynes

Abstract: As part of an investigation into new synthetic routes to poly(peri-naphthalene), the synthesis and cycloaromatization of tetraethynylbiphenyls is described. The temperature-dependent cyclization of biphenyls containing unsubstituted alkynes provides the desired perylene in good yield.

Cited by 18 publications

References 21 publications

(Hetero)aromatics from dienynes, enediynes and enyne–allenes

(Hetero)aromatics from dienynes, enediynes and enyne–allenes

Triazole: a unique building block for the construction of functional materials

Palladium‐Catalyzed CC Bond Formation

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