Anthracen‐Derivate mit N‐ und O‐Brückenatom

Wittig, Georg; Stilz, W.; Knauss, Erhard

doi:10.1002/ange.19580700611

Cited by 3 publications

(3 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…To synthesize triptycene 1 a , cycloaddition reactions between anthracenes 2 and benzynes 3 are commonly utilized (Scheme a1). The conventional method focuses mainly on the preparation of arynes, and the easily available benzyne precursors do not always provide triptycenes efficiently …”

Section: Methodsmentioning

confidence: 99%

Anthranoxides as Highly Reactive Arynophiles for the Synthesis of Triptycenes

Iwata

Hyodo

Fukami

et al. 2020

Chemistry A European J

View full text Add to dashboard Cite

We report herein ane fficient methodt os ynthesize triptycenes by the reaction of benzynes and anthranoxides, whicha re electron-richa nd readily prepared from the corresponding anthrones. Using this method, 1,9-synsubstituted triptycenes were regioselectivelyo btained employing 3-methoxybenzynes. This methodw as also applied to synthesize pentiptycenes. AD FT study revealed that the cycloaddition of lithium anthranoxide and benzyne proceeds stepwise. Triptycenes 1, [1] whichc onsist of an arene-fused bicyclo[2,2,2]octatriene bridgehead system,a re aromatic compounds with at hree-dimensional rigid molecular structure. Based on this unique structure, triptycenes are widely used in the field of molecular recognition, [2] molecular machine, [3] supramolecular chemistry, [4] materials science [5] and as metal ligands. [6] To synthesize triptycene 1a,c ycloaddition reactions between anthracenes 2 and benzynes 3 [7] are commonly utilized (Scheme 1a1). The conventionalm ethod focusesm ainly on the preparation of arynes, [8] and the easily availableb enzyne precursors do not alwaysp rovide triptycenes efficiently. [8a-f] Therefore, the use of more reactive arynophiles is one way to resolve this drawback, but this was not sufficiently investigateds of ar.I nl iterature, af ew electron-rich anthracenes [9] such as 9-acetoxyanthracenes, [9c,e] 9-methoxyanthracenes, [9a,d,f] and 1,4-dioxysulfonylanthracenes [9i] were appliedi nt riptycene syntheses. These anthracenes,h owever,u sually requireamultistep preparation, are less reactive [9e,h] or are easily oxidized and not isolated in pure form. [9g,i] Thus, it is desirable to develop anthracenes which are sufficiently reactive and easily handled. Recently,w edevelopedanovel one-pot synthesis of triptycenes 1b using at riple cycloaddition of benzynes to ynolates [10] 4 (Scheme 1b). [11] The key of this reactioni st he in situ generation of anthranoxides 6 by ad ouble [2+ +2] cycloaddition of ynolates 4 with two equivalents of benzynes followed by fragmentation of the resulting Dewar anthracenes 5.T he anthranoxides 6 subsequently reactedw ith the third equivalent of benzyne in a[ 4 + +2] cycloaddition.I na ddition, using 3-methoxy-[11a] or 3-silylbenzynes, sterically congested 1,8,13-trifunctionalized triptycenes 1b were selectively obtainedw here three methoxy or silyl groups were located at the same side of the C9-hydroxyl group. Duringt hese studies, we noticed that anthranoxide 6 is ah ighly reactive arynophile for the [4+ +2] cycloaddition due to the strong electron-donating effect of the Scheme1.Synthetic methods of triptycene.

show abstract

Section: Methodsmentioning

confidence: 99%

Anthranoxides as Highly Reactive Arynophiles for the Synthesis of Triptycenes

Iwata

Hyodo

Fukami

et al. 2020

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…The benzyne intermediate reacts with other dienes to produce adducts in good yield (112). Thus cyclopentadiene reacts to produce 1,4-endomethylene-l ,4-dihydronaphthalene in 65% yield (124); also with A-methylisoindole and 1,3-diphenylisobenzofuran to produce 9,10 -endo -Nmethylamine -9,10 -dihydroanthracene (54%) and 9,10-epoxy-9,10-diphenyl-9,10-dihydroanthracene (85%), respectively (133).…”

Section: O' + ° -mentioning

confidence: 99%

The Benzyne and Related Intermediates.

Heaney¹

1962

Chem. Rev.

160

View full text Add to dashboard Cite

“…The triptycene fragment is generally obtained by a [4+2] cycloaddition of a benzyne species (prepared in situ) onto an anthracene unit 18. Benzynes can be obtained by reaction of magnesium with 1‐bromo‐2‐fluorobenzene,18 reaction of BuLi with fluorobenzene,19 from oxadisilols,20 from iodonium ortho ‐benzoate,18 or by reaction of anthranilic acid with isopentyl nitrite 7b. By modification of a published procedure,21 we used this latter method to obtain 1 in three steps from commercially available 9,10‐dibromoanthracene.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Functionalized Mono‐, Bis‐, and Trisethynyltriptycenes for One‐Dimensional Self‐Assembly on Surfaces

Sirven

Garbage

Qiao

et al. 2015

Chemistry A European J

View full text Add to dashboard Cite

This paper describes the synthesis of triptycene-based building blocks that are able to interact through hydrogen bonds to form one-dimensional self-assembled motifs on surfaces. We designed 9,10-diethynyltriptycene derivatives functionalized at the ethynyl end groups by a variety of hydrogen-bonding groups for homomolecular recognition and complementary building blocks for heteromolecular recognition. We also present the synthesis of bis- and trisethynyltriptycenes with terminal alkyne functional groups available for on-surface azide-alkyne cycloaddition reaction to expand the potential of the triptycene building block.

show abstract

Anthracen‐Derivate mit N‐ und O‐Brückenatom

Cited by 3 publications

References 1 publication

Anthranoxides as Highly Reactive Arynophiles for the Synthesis of Triptycenes

Anthranoxides as Highly Reactive Arynophiles for the Synthesis of Triptycenes

The Benzyne and Related Intermediates.

Synthesis of Functionalized Mono‐, Bis‐, and Trisethynyltriptycenes for One‐Dimensional Self‐Assembly on Surfaces

Contact Info

Product

Resources

About