Improved Synthesis of Enantiopure 4-Hydroxy[2.2]paracyclophane

Friedmann, Christian; Ay, Sefer; Bräse, Stefan

doi:10.1021/jo100468s

Cited by 52 publications

(48 citation statements)

References 40 publications

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“…Rozenberg et al developed a route to acetyl‐hydroxy[2.2]paracyclophane (AHPC, 9 ), which is one of the intermediate structures towards hydroxy‐pyrazolyl[2.2]paracyclophanes 18. In this three‐step, racemic sequence, with a total yield of 62 %, AHPC ( 9 ) is accessible from formyl[2.2]paracyclophane (Rieche formylation) and subsequent hydroxy[2.2]paracyclophane (Dakin oxidation) 19…”

Section: Resultsmentioning

confidence: 99%

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Roadmap towards N‐Heterocyclic [2.2]Paracyclophanes and Their Application in Asymmetric Catalysis

et al. 2013

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A novel family of [2.2]paracyclophane derivatives is described. Different substituted pyrazole, triazole and pyrimidine moieties were introduced to the [2.2]paracyclophane scaffold and the products were characterized spectroscopically and by X‐ray structure analysis. These compounds are promising ligands for application in asymmetric catalysis. We show here that one of these ligands can catalyze asymmetric conjugate addition. Furthermore a palladium complex was synthesized by using a hydroxy‐pyrazolyl[2.2]paracyclophane ligand.

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Section: Resultsmentioning

confidence: 99%

“…The yield of 11i was too low to continue with this compound as the model catalyst. Therefore, synthesis of ( S p )‐ 11h , bearing a t Bu group on the pyrazole, was carried out starting from enantiopure ( S p )‐formyl[2.2]paracyclophane,19 following the steps described earlier (Schemes and ).…”

Section: Resultsmentioning

confidence: 99%

Roadmap towards N‐Heterocyclic [2.2]Paracyclophanes and Their Application in Asymmetric Catalysis

et al. 2013

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“…Thus we assume 1 crystallizes as racemic conglomerate . It is worth noting that due to an efficient methodology for the resolution of racemic formyl[2.2]paracyclophane, the phosphine L1 can be obtained in a highly enantioenriched form, which enables a straightforward synthesis of an enantioenriched gold complex.…”

Section: Resultsmentioning

confidence: 99%

Double‐Strand DNA Breaks Induced by Paracyclophane Gold(I) Complexes

Bestgen

Seidl

Wiesner

et al. 2017

Chemistry A European J

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Gold(I) complexes of ClickPhos [2.2]paracyclophane ligands were synthesized in excellent yields and fully characterized by spectroscopic methods as well as X-ray crystallography. The complexes exhibit a rigid ligand backbone and a triazolyl moiety and were systematically studied with respect to their cytotoxic properties. In combination with the ionic complex [(GemPhos)Au(tht)][ClO ] (tht=tetrahydrothiophene), in which the gold(I) atom exhibits a distorted trigonal coordination sphere of two phosphines and a labile tht ligand, their efficiency in cytotoxicity was investigated in HeLa, MCF7, and HCT116 cells as well as in a zebrafish model. Their cytotoxicity and their mechanisms of action are different and involve apoptosis, necrosis, and DNA damage. The compounds presented herein are potent metal-based cytostatics displaying LD values from 3.5-38 μm in different tumor cell lines and induce double-strand DNA breaks (DSB) as shown by H2AX phosphorylation (γH2AX) at foci of DSBs.

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“…Starting from inexpensive, commercially available [2.2]paracyclophane ( 4 ), the O ‐methylaldoxime 1 was easily obtained in only two steps and almost quantitative yield by following a reported formylation procedure10 and subsequent conversion with methoxylamine hydrochloride (Scheme , a). Notably, O ‐methyloxime ( S p )‐ 1 was also synthesized in enantiopure form from enantiopure formyl[2.2]paracyclophane ( S p )‐ 5 (FPC) to provide access to enantiopure ortho ‐disubstituted [2.2]paracyclophanes.…”

Section: Resultsmentioning

confidence: 99%

Direct Access to 4,5‐Disubstituted [2.2]Paracyclophanes by Selective ortho‐Halogenation with Pd‐Catalyzed C–H Activation

et al. 2013

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A palladium‐catalyzed protocol for the halogenation of [2.2]paracyclophanes by C–H activation is described, and ortho selectivity is achieved with an O‐methyloxime directing group. Bromination and iodination of the sterically demanding [2.2]paracyclophane proceed in good yields with inexpensive and readily available N‐halosuccinimides. Deprotection of the O‐methyloximes yields ortho‐halogenated aldehydes as attractive intermediates for the modular synthesis of 4,5‐disubstituted [2.2]paracyclophanes. The synthetic value of this protocol was demonstrated by exemplary conversions of the carbaldehyde and halogen site. Additionally, early stage resolution and subsequent bromination/deprotection provides the brominated aldehyde in enantiopure form.

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Improved Synthesis of Enantiopure 4-Hydroxy[2.2]paracyclophane

Cited by 52 publications

References 40 publications

Roadmap towards N‐Heterocyclic [2.2]Paracyclophanes and Their Application in Asymmetric Catalysis

Roadmap towards N‐Heterocyclic [2.2]Paracyclophanes and Their Application in Asymmetric Catalysis

Double‐Strand DNA Breaks Induced by Paracyclophane Gold(I) Complexes

Direct Access to 4,5‐Disubstituted [2.2]Paracyclophanes by Selective ortho‐Halogenation with Pd‐Catalyzed C–H Activation

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