Synthesis of Bromo‐Substituted 4‐Hydroxy[2.2]paracyclophanes and [2.2]Paracyclophane‐4,7‐quinones as Versatile Chiral Building Blocks

The structure of the products formed upon oxidation of 4‐hydroxy[2.2]paracyclophane and its derivatives with Cu(OH)Cl·TMEDA depends on the solvent used. In MeOH oxidation accompanied with nucleophilic attack of the solvent to furnish predominantly or exclusively ortho‐cyclohexadienones (o‐quinol methyl ethers) of (Rp*,Rp*) relative configuration. Oxidation carried out in CH2Cl2 results in regio‐ and stereoselective formation of para‐cyclohexadienone dimers {variously substituted 7,7′‐bis[2.2]paracyclophan‐4,4′(7H,7′H)‐diones} with (Sp*,Rc*,Rc*,Sp*) relative and (Rp,Sc,Rc,Sp) absolute configurations (two out of six possible diastereomers in each case), whereas oxidation of the enantiomerically pure phenol produced the respective single product. The dimeric cyclohexadienones can suffer aromatization to form the respective dimeric para‐biphenols under the action of KOH in EtOH.

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Solvent‐Dependent Regio‐ and Stereoselective Oxidation of [2.2]Paracyclophane‐Derived Phenols

Zhuravsky

Antonov

Сергеева

et al. 2016

Eur J Org Chem

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Regioselective Synthesis of 4,7,12,15‐Tetrasubstituted [2.2]Paracyclophanes: A Modular Route Involving Optical Resolution

Biliz

Çakıcı

2021

Eur J Org Chem

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A practical synthetic method for preparing bis‐(para)‐pseudo‐ortho and bis‐(para)‐pseudo‐meta type 4,7,12,15‐tetrasubstituted [2.2]paracyclophanes is reported. Regioselective double Rieche formylation was successfully applied to the corresponding dibromo[2.2]paracyclophanes under slightly modified conditions. Aldehydes reacted in an unknown direction with Rieche formylation agents, dichloromethyl methyl ether and titanium(IV) tetrachloride, leading to the formation of benzal chlorides. Formylated products were obtained after hydrolysis of these benzal chloride derivatives. Optical resolution was performed with the diastereomer method and (RP)‐4,12‐dibromo‐7,15‐diformyl[2.2]paracyclophane was successfully obtained in an enantiomerically pure form (99 % ee). Their synthetic utility is demonstrated with some exploratory transformations to access corresponding differently functionalized tetrasubstituted [2.2]paracyclophane derivatives.

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Synthesis of Bromo‐Substituted 4‐Hydroxy[2.2]paracyclophanes and [2.2]Paracyclophane‐4,7‐quinones as Versatile Chiral Building Blocks

Cited by 2 publications

References 53 publications

Solvent‐Dependent Regio‐ and Stereoselective Oxidation of [2.2]Paracyclophane‐Derived Phenols

Solvent‐Dependent Regio‐ and Stereoselective Oxidation of [2.2]Paracyclophane‐Derived Phenols

Regioselective Synthesis of 4,7,12,15‐Tetrasubstituted [2.2]Paracyclophanes: A Modular Route Involving Optical Resolution

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Synthesis of Bromo‐Substituted 4‐Hydroxy[2.2]paracyclophanes and [2.2]Paracyclophane‐4,7‐quinones as Versatile Chiral Building Blocks

Cited by 2 publications

References 53 publications

Solvent‐Dependent Regio‐ and Stereo­selective Oxidation of [2.2]Para­cyclophane‐Derived Phenols

Solvent‐Dependent Regio‐ and Stereo­selective Oxidation of [2.2]Para­cyclophane‐Derived Phenols

Regioselective Synthesis of 4,7,12,15‐Tetrasubstituted [2.2]Paracyclophanes: A Modular Route Involving Optical Resolution

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Product

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Solvent‐Dependent Regio‐ and Stereoselective Oxidation of [2.2]Paracyclophane‐Derived Phenols

Solvent‐Dependent Regio‐ and Stereoselective Oxidation of [2.2]Paracyclophane‐Derived Phenols