DMAP‐[2.2]paracyclophane: Observation of an Unusual C–C Insertion

Rycke, Nicolas de; Marrot, Jérôme; Couty, François; David, Olivier

doi:10.1002/ejoc.201001623

Cited by 6 publications

(2 citation statements)

References 47 publications

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“…But the upfield signal at 5.80 ppm, along with the unusual splitting of the bridgehead protons (H1, 2, 9 and 10) was unlike any [2.2]paracyclophane derivative we had observed. It was clear that we had isolated a cyclophane, but we suspected rearrangement [ 61 – 62 ]. The structure of the other side-product, 6 , was even harder to determine due to the lack of characteristic high field aromatic proton signals.…”

Section: Resultsmentioning

confidence: 99%

Breaking paracyclophane: the unexpected formation of non-symmetric disubstituted nitro[2.2]metaparacyclophanes

Patel¹,

Dais²,

Plieger³

et al. 2021

Beilstein J. Org. Chem.

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Substituted [2.2]metaparacyclophanes are amongst the least studied of the simple cyclophanes. This is undoubtedly the result of the lengthy syntheses of these compounds. We report the simple synthesis of a rare example of a non-symmetric [2.2]metaparacyclophane. Treatment of [2.2]paracyclophane under standard nitration conditions gives a mixture of 4-nitro[2.2]paracyclophane, 4-hydroxy-5-nitro[2.2]metaparacyclophane and a cyclohexadienone cyclophane.

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Section: Resultsmentioning

confidence: 99%

Breaking paracyclophane: the unexpected formation of non-symmetric disubstituted nitro[2.2]metaparacyclophanes

Patel¹,

Dais²,

Plieger³

et al. 2021

Beilstein J. Org. Chem.

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“…The issue of diminished catalyst efficiency applies to DMAP or PPY derivatives that carry a ring that connects the C2 and C3 carbons of the pyridyl ring ( Fig. 1d ) 22 . In most cases, diminished stability of the key ion-pair intermediate because of steric repulsion between substituents and 4-amino moiety and/or N -acetyl group was a complication 21 .…”

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confidence: 99%

Enantioselective acyl transfer catalysis by a combination of common catalytic motifs and electrostatic interactions

et al. 2016

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Catalysts that can promote acyl transfer processes are important to enantioselective synthesis and their development has received significant attention in recent years. Despite noteworthy advances, discovery of small-molecule catalysts that are robust, efficient, recyclable and promote reactions with high enantioselectivity can be easily and cost-effectively prepared in significant quantities (that is, >10 g) has remained elusive. Here, we demonstrate that by attaching a binaphthyl moiety, appropriately modified to establish H-bonding interactions within the key intermediates in the catalytic cycle, and a 4-aminopyridyl unit, exceptionally efficient organic molecules can be prepared that facilitate enantioselective acyl transfer reactions. As little as 0.5 mol% of a member of the new catalyst class is sufficient to generate acyl-substituted all-carbon quaternary stereogenic centres in quantitative yield and in up to 98:2 enantiomeric ratio (er) in 5 h. Kinetic resolution or desymmetrization of 1,2-diol can be performed with high efficiency and enantioselectivity as well.

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A Novel Carbazolophane: A Comparison of the Performance of Two Planar Chiral CP‐TADF Emitters

Seibert,

Xu,

Hafeez

et al. 2024

Adv Funct Materials

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The prototypical example of a (cyclo)phane, [2.2]paracyclophane (PCP), has proven to be a versatile stereogenic moiety within the design of circularly polarized thermally activated delayed fluorescence (CP‐TADF) emitters; however, the exploration of other cyclophanes within CP‐TADF emitter design has been largely neglected. Here, a comparative study of the photophysical and optoelectronic properties of two cyclophane emitters, (1,7)tBuCzpPhTrz and its isomer (1,4)tBuCzpPhTrz, is presented. The carbazolophane‐triazine compound (1,7)tBuCzpPhTrz, obtained via an unprecedented intramolecular rearrangement, is the first example of a planar chiral TADF emitter deviating from the PCP scaffold. Significant geometrical change of the enclosed carbazole in (1,7)tBuCzp results in an attenuation of the donor strength, while the merits of rigidity and steric bulk remain. In particular, the full width at half maximum (FWHM) of the photoluminescence spectrum in toluene of (1,7)tBuCzpPhTrz is reduced by 34% and blue‐shifted by 20 nm compared to that of (1,4)tBuCzpPhTrz. In doped films, the compounds reach high photoluminescence quantum yields (ΦPL) of 91 and 81%, respectively. The chiroptical properties reveal dissymmetry factors |gPL| of up to 5 × 10−4. These results demonstrate the impact of the cyclophane for the development of CP‐TADF materials and add to the currently limited scope of available planar chiral donors.

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DMAP‐[2.2]paracyclophane: Observation of an Unusual C–C Insertion

Cited by 6 publications

References 47 publications

Breaking paracyclophane: the unexpected formation of non-symmetric disubstituted nitro[2.2]metaparacyclophanes

Breaking paracyclophane: the unexpected formation of non-symmetric disubstituted nitro[2.2]metaparacyclophanes

Enantioselective acyl transfer catalysis by a combination of common catalytic motifs and electrostatic interactions

A Novel Carbazolophane: A Comparison of the Performance of Two Planar Chiral CP‐TADF Emitters

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