24262-20-2

Upstream product

• 1633-22-3 [2.2]Paracyclophan 
• 383191-69-3 4,12-dihydroxy-5,13-dipentanoyl[2.2]paracyclophane 
• 36325-27-6 4-formyl[2.2]paracyclophane 
• 301817-11-8 4,12-bis(formyl)[2.2]paracyclophane 
• 196316-30-0 4,16-dibromo[2.2]paracyclophane 

Downstream Products

• 612492-27-0 (R)-(+)-4,12-dihydroxy[2.2]paracyclophane 
• 612492-27-0 (S)-(-)-4,12-dihydroxy[2.2]paracyclophane 
• 612492-27-0 (S_p)-(-)-4,12-dihydroxy-[2.2]paracyclophane 
• 612492-27-0 (R_p)-4,12-dihydroxy[2.2]paracyclophane 
• 5628-11-5 4-hydroxy-[2,2]-paracyclophane 
• 157018-15-0 (R_p)-(+)-4-hydroxy-[2.2]paracyclophane 

Relevant academic research and scientific papers

A curious benzenoid deacylation reaction: Neighbouring group participation in acylhydroxy[2.2]paracyclophanes

Attempted carbonyl reduction of acyldihydroxy[2.2]paracyclophanes with sodium borohydride led instead to competing aromatic deacylation. The effect was traced to a neighbouring group participation that can be correlated with carbonyl IR stretching frequencies. Deuterium labelling studies implicate the formal intermediacy of a solvated [2.2]paracyclophane anion via an SE1 mechanism.

Tuning the Reactivity of Peroxo Anhydrides for Aromatic C-H Bond Oxidation

Phenol moieties are key structural motifs in many areas of chemical research from polymers to pharmaceuticals. Herein, we report on the design and use of a structurally demanding cyclic peroxide (spiro[bicyclo[2.2.1]heptane-2,4′-[1,2]dioxolane]-3′,5′-dione, P4) for the direct hydroxylation of aromatic substrates. The new peroxide benefits from high thermal stability and can be synthesized from readily available starting materials. The aromatic C-H oxidation using P4 exhibits generally good yields (up to 96%) and appreciable regioselectivities.

Highly Efficient Kinetic Resolution of PHANOL by Chiral Phosphoric Acid Catalyzed Asymmetric Acylation

We report herein a highly efficient kinetic resolution of PHANOL by chiral phosphoric acid catalyzed asymmetric acylation. PHANOL enantiomers were well differentiated by the chiral environment of chiral phosphoric acid, and both the corresponding monoester and PHANOL were obtained with excellent enantioselectivities (98% ee and 92% ee, respectively). Detailed examination of the substrates suggests that the presence of two hydroxy groups in PHANOL was critical for both reactivity and enantioselectivity.

Photochromism of novel chromenes constrained to be part of [2.2]paracyclophane: Remarkable 'phane' effects on the colored o-quinonoid intermediates

The photochemistry of rationally designed chromenes that are constrained to be part of [2.2]paracyclophane, i.e., CP-H and CP-OMe, was investigated to examine the effect of through-space delocalization in the cyclophane core (phane effect) on the photochr

Synthesis, chiral resolution, and absolute configuration of dissymmetric 4,12-difunctionalized [2.2]paracyclophanes

Racemic 4,12-difunctionalized [2.2]paracyclophanes were synthesized and successfully resolved by (recycling) HPLC on a stationary CHIRALPAK IA phase at a semipreparative scale. Their absolute configurations were determined by X-ray crystal structure analy

Symmetrically tetrasubstituted [2.2]paracyclophanes: Their systematization and regioselective synthesis of several types of bis-bifunctional derivatives by double electrophilic substitution

The possible number of chiral and achiral tetrasubstituted [2.2]paracyclophanes possessing different types of symmetry (C2, Ci, Cs, C2., C2h) is evaluated and a unified independent trivial naming descriptor system is introduced. The reactivity and regioselectivity of the electrophilic substitution of the chiral pseudo-mefaand achiral pseudo-para-disubstituted [2.2]paracyclophanes are investigated in an approach suggested to be general for the synthesis of bis-bifunctional [2.2]paracyclophanes. The mono- and diacylation of chiral pseudo-meta-dihydroxy[2.2]paracyclophane 14 with acetylchloride occur ortho-regioselectively to produce tri- 22, 23 and symmetrically 21 tetrasubstituted acyl derivatives. The same reaction with benzoylchloride is neither regio-, nor chemoselective, and gives rise to a mixture of ortho-lpara-, mono-/diacylated compounds 27-31. The double acylation of pseudo-meta- dimethoxy[2.2]paracyclophane 18 is completely para-regioselective. Electrophilic substitution of pseudo-wera-bis(methoxycarbonyl)[2.2]paracyclophane 20 regioselectively generates the pseudo-gem-substitution pattern. Formylation of this substrate produces the monocarbonyl derivatives 35 only, whereas the Fe-catalyzed bromination may be directed towards mono- 36 or disubstitution 37 products chemoselectively by varying the reactions conditions. The diacylation and dibromination reactions of the respective achiral diphenol 12 and bis(methoxycarbonyl) 40 derivatives of the pseudo-para-structure retain regioselectivities which are characteristic for their pseudo-mefa-regioisomers. Imino ligands 26, 25, and 39, which were obtained from monoacyl- 22 and diacyldihydroxy[2.2]paracyclophanes 21, 38, are tested as chiral ligands in stereoselective Et2Zn addition to benzaldehyde producing 1-phenylpropanol with ee values up to 76%.

Planar chiral PHANOLS as organocatalysts for the Diels-Alder reaction via double hydrogen-bonding to a carbonyl group

Planar chiral PHANOLs have been shown to catalyze Diels-Alder reactions of α,β-unsaturated aldehydes and ketones with various dienes. Rate accelerations of up to ca. 30-fold were obtained using the electron deficient 4,12-dihydroxy-7,15-dinitro[2.2]paracyclophane as a catalyst. It is proposed that the carbonyl group of the dienophile is activated via a double hydrogen-bonding mode. Although the PHANOLs are inherently chiral, little or no asymmetric induction was observed when using enantiopure (R)-PHANOL.

Improved synthesis of (±)-4,12-dihydroxy[2.2]paracyclophane and Its enantiomeric resolution by enzymatic methods: Planar chiral (R)- and (S)-phanol

(±)-4,12-Dihydroxy[2.2]paracyclophane [(±)-PHANOL] is readily prepared from [2.2]paracyclophane by an improved synthetic protocol. Enzymatic kinetic resolution of its bis-acetate proceeds with good enantioselection. Separation, hydrolysis, and recrystallization provides both enantiomers of PHANOL in high enantiopurity.