Synthesis of an ortho-Triazacyclophane: N,N′,N′′-Trimethyltribenzo-1,4,7-triazacyclononatriene

Panagopoulos, Andria M.; Zeller, Mat­thias; Becker, Daniel P.

doi:10.1021/jo1017074

Cited by 23 publications

(26 citation statements)

References 46 publications

(51 reference statements)

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“…The first method employed a Buchwald-Hartwig N-arylation, [10][11][12][13] which was ultimately successful in the macrocyclization of 3a to azacyclophane 2a. 9 In parallel, we had also envisioned that the use of benzyne (aryne) intermediate 4a should be a viable synthetic route to the triazacyclophane skeleton, which led to the observation of an unexpected alkyl transfer and phenazine formation with interesting mechanistic implications that we describe herein. Since then, aryne intermediates have been used extensively in organic synthesis 16 and in the synthesis of natural products.…”

Section: Introductionmentioning

confidence: 84%

Apparent Alkyl Transfer and Phenazine Formation via an Aryne Intermediate

et al. 2013

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Treatment of chlorotriaryl derivatives 3a and 3d or fluorotriaryl derivatives 3b and 3e with potassium diisopropylamide afforded alkyl-shifted phenazine derivatives 5a/5b, rather than the expected 9-membered triaza orthocyclophane 2a. The phenazine derivatives were isolated in 78-98% yield depending on the halogen and alkyl group present. In the absence of the halogen (chloro or fluoro), the apparent alkyl shift proceeds more slowly and cannot proceed via, the intermediacy of the aryne

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Section: Introductionmentioning

confidence: 84%

Apparent Alkyl Transfer and Phenazine Formation via an Aryne Intermediate

et al. 2013

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“…However, the crown-like conformation required to coordinate the metal is 12.9 kcal/mol (OPBE/cc-pVTZ PCM water, detail in Paper IV) higher than that of the crystallized N,N'-dimethylated analogous. 258 The latter conformation does not allow tridentate N-coordination of the metal, thus, although the evolved populations of both…”

Section: Resultsmentioning

confidence: 99%

Automated Design of Realistic Organometallic Molecules from Fragments

Foscato

Occhipinti

Venkatraman

et al. 2014

J. Chem. Inf. Model.

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A method for the automated generation of realistic, synthetically accessible transition metal and organometallic complexes is described. Computational tools were designed to generate molecular fragments, preferably harvested from libraries of existing, stable compounds, to be used as building blocks for the construction of new molecules. These fragments are enriched with information about the number and type of possible connections to other fragments and are stored in library files. When connecting fragments in the subsequent building process, compatibility matrices, which define the connection rules between fragments, are used to delineate organometallic fragment spaces from which molecules can be generated in an automated fashion. The approach is flexible and allows ample structural variation at the same time as the combination of known fragments is easily restrained to avoid generation of exotic and unrealistic substructures and molecules. The method was tested in the generation of ruthenium complexes, with a given coordination environment, which can serve as candidates in catalyst development. The results demonstrate that molecules generated with the described method do not contain exotic arrangements of atoms and are by far more realistic than those obtained by the application of valence rules alone.

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“…Part of our research program is focused on the construction of apex-modified derivatives [15][16][17] of the trimeric crown-shaped (bowl-shaped) [1.1.1]orthocyclophane cyclotriveratrylene 1 (CTV, Figure 2) 18 with applications in host-guest chemistry. 19 Trans-annular rearrangements are known to occur when attempting to oxidize CTV-5,10-dione 1c to the corresponding triketone which leads to rearrangement to the spiro derivative 2, 20, 21 and we have observed a trans-annular electrophilic aromatic addition or substitution cascade following a Beckmann rearrangement reaction on a related system.…”

Section: Resultsmentioning

confidence: 99%

Rearrangement of Cyclotriveratrylene (CTV) Diketone: 9,10-Diarylanthracenes with OLED Applications

et al. 2012

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Electroluminescent 9,10-diaryl anthracenes have been shown to be promising host and hole-transporting materials in organic electroluminescence due to their high thermal stability, electrochemical reversibility and wide band gap useful for organic light emitting diodes (OLEDs), especially blue OLEDs. Oxidation of cyclotriveratrylene (CTV) to the corresponding diketone and subsequent bromination resulted in an unexpected rearrangement to a highly functionalized 9-aryl-10-bromoanthracene derivative, which was employed in Suzuki couplings to synthesize a series of 9,10-diaryl compounds that are structural analogs of anthracene derivatives used in the preparation of OLEDs, but are more highly functionalized, including electron-donating methoxy groups in addition to substitution by a carboxylic acid moiety. The UV/fluorescence solution spectra show strong emissions at a 446 nm, 438 nm and 479 nm, respectively, for the anthracene 10-phenyl, 10-naphthyl and 10-pyrenyl adducts containing a benzoic acid functional group, whereas the analogs bearing the hydroxymethylene moiety from reduction of the benzoic acid to the corresponding alcohols gave much shorter emission wavelengths of 408 nm, 417 nm, and 476 nm, respectively, and had somewhat higher quantum yields, suggesting they are better candidates for OLED applications.

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Synthesis of an ortho-Triazacyclophane: N,N′,N′′-Trimethyltribenzo-1,4,7-triazacyclononatriene

Cited by 23 publications

References 46 publications

Apparent Alkyl Transfer and Phenazine Formation via an Aryne Intermediate

Apparent Alkyl Transfer and Phenazine Formation via an Aryne Intermediate

Automated Design of Realistic Organometallic Molecules from Fragments

Rearrangement of Cyclotriveratrylene (CTV) Diketone: 9,10-Diarylanthracenes with OLED Applications

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