Diels–Alder reactions of arynes in situ generated from DA reaction between bis-1,3-diynes and alkynes

Zhang, Mingxing; Shan, Wei Guang; Chen, Zhao; Yin, Jun; Yu, Guang‐Ao; Liu, Sheng Hua

doi:10.1016/j.tetlet.2015.10.076

Cited by 23 publications

(8 citation statements)

References 38 publications

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“…Here we describe a new strategy for carbazole assembly that capitalizes on the hexadehydro-Diels–Alder (HDDA) cascade . The process involves a sequential net 4+2 cycloisomerization reaction between a 1,3-diyne and a diynophile to produce a benzyne intermediate, followed by one of several different modes of trapping reactions. − This cascade constitutes a powerful and versatile strategy for synthesis of benzenoid derivatives in which the benzene ring itself has been assembled in de novo fashion from the six reacting alkyne carbon atoms. The purely thermal nature of the reaction conditions lends itself to the discovery of new types of aryne trapping reactions that can be complementary to those possible with arynes generated by conventional means.…”

mentioning

confidence: 99%

Hexadehydro-Diels–Alder (HDDA)-Enabled Carbazolyne Chemistry: Single Step, de Novo Construction of the Pyranocarbazole Core of Alkaloids of the Murraya koenigii (Curry Tree) Family

Wang

Hoye

2016

J. Am. Chem. Soc.

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Here we report the use of the hexadehydro-Diels–Alder (HDDA) reaction for the de novo construction of a benzenoid ring in fused polycyclic heteroaromatic carbazole (i.e., [2,3]-benzoindole) skeletons. The strategy allows creation of highly substituted benzenoids. We also describe the HDDA-enabled chemical synthesis of the natural product alkaloids mahanimbine and koenidine. Trapping of the intermediate carbazolyne with a conjugated enal–proceeding through formal [2+2] cycloaddition, 4π-electrocyclic ring-opening, and 6π-electrocyclic ring-closing events—constitutes a robust method for producing pyranocarbazoles.

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confidence: 99%

Hexadehydro-Diels–Alder (HDDA)-Enabled Carbazolyne Chemistry: Single Step, de Novo Construction of the Pyranocarbazole Core of Alkaloids of the Murraya koenigii (Curry Tree) Family

Wang

Hoye

2016

J. Am. Chem. Soc.

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“…Accordingly, one of the early reactions we explored was that between the tetrayne 9a and TPCP ( 3 , Figure ). The symmetry of this HDDA substrate make it attractive from a preparative perspective. It is made in two simple steps .…”

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confidence: 99%

Blue-Emitting Arylalkynyl Naphthalene Derivatives via a Hexadehydro-Diels–Alder Cascade Reaction

Hershey

Holmes

et al. 2016

J. Am. Chem. Soc.

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We describe here three alkynyl substituted naphthalenes that display promising luminescence characteristics. Each compound is easily and efficiently synthesized in three steps by capitalizing on the hexadehydro-Diels–Alder (HDDA) cycloisomerization reaction in which an intermediate benzyne is captured by tetraphenylcyclopentadienone, a classical trap for benzyne itself. These compounds luminesce in the deep blue when stimulated either optically (i.e., photoluminescence in both solution and solid films) or electrically [in a light-emitting diode (LED)]. The photophysical properties are relatively insensitive to the electronic nature of the substituents (H, OMe, CO2Me) that define these otherwise identical compounds. Overall, our observations suggest that the twisted nature of the five adjacent aryl groups serves to minimize the intermolecular interaction between core naphthalene units in different sample morphologies. These compounds represent promising leads for the identification of others of value as the emissive component of organic LEDs (OLEDs).

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“…The hexadehydro-Diels-Alder reaction, by which benzyne intermediates (Niu et al, 2013) as well as highly functionalized benzenoid products (Karmakar et al, 2013) are prepared, has played a very significant role in the field of organic synthesis. Zhang et al (2015) observed that benzyne intermediates can be captured by five-membered heterocyclic compounds, such as furans, pyrroles and thiophenes. As part of our work on the application of the hexadehydro-Diels-Alder reaction (Meng et al, 2017), we report herein the synthesis and crystal structure of the title compound.…”

Section: Chemical Contextmentioning

confidence: 99%

“…rings are in an envelope conformation and the benzene rings in each fused ring system show a similar dihedral angle of ca 72 . A search for structures with a 3,6,7,8-tetrahydro-1Hindeno[4,5-c]furan fragment revealed two hits, and one of the compounds, dimethyl 5-phenyl-4-(phenylethynyl)-1,3,6,9tetrahydro-2H-6,9-epoxycyclopenta[a]naphthalene-2,2-dicarboxylate (refcode IKOJUP; Zhang et al, 2015) is closely related to the title compound.…”

Section: Figurementioning

confidence: 99%

Crystal structure of dimethyl 5-(4-ethylphenyl)-4-[(4-ethylphenyl)ethynyl]-6,11-diphenyl-1,3,6,11-tetrahydro-2H-6,11-epoxycyclopenta[a]anthracene-2,2-dicarboxylate

Meng¹,

Cheng²

2020

Acta Cryst E

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In the central fused ring system of the title compound, C51H42O5, all of the five-membered rings are in an envelope conformation. The dihedral angle between the two benzene rings in the fused ring system is 74.66 (7)°. In the crystal, molecules are linked by C—H...π interactions, forming a layer parallel to the ab plane. Each molecule acts as a double donor as well as a double acceptor of the C—H...π interactions. Hirshfeld surface analysis and two-dimensional fingerprint plots indicate that the most important contributions to the crystal packing are from H...H (61.4%) and C...H/H...C (25.3%) contacts.

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Diels–Alder reactions of arynes in situ generated from DA reaction between bis-1,3-diynes and alkynes

Cited by 23 publications

References 38 publications

Hexadehydro-Diels–Alder (HDDA)-Enabled Carbazolyne Chemistry: Single Step, de Novo Construction of the Pyranocarbazole Core of Alkaloids of the Murraya koenigii (Curry Tree) Family

Hexadehydro-Diels–Alder (HDDA)-Enabled Carbazolyne Chemistry: Single Step, de Novo Construction of the Pyranocarbazole Core of Alkaloids of the Murraya koenigii (Curry Tree) Family

Blue-Emitting Arylalkynyl Naphthalene Derivatives via a Hexadehydro-Diels–Alder Cascade Reaction

Crystal structure of dimethyl 5-(4-ethylphenyl)-4-[(4-ethylphenyl)ethynyl]-6,11-diphenyl-1,3,6,11-tetrahydro-2H-6,11-epoxycyclopenta[a]anthracene-2,2-dicarboxylate

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