<i>C</i><sub>3</sub>-Symmetrical Tribenzotriquinacene Derivatives: Optical Resolution through Cryptophane Synthesis and Supramolecular Self-Assembly into Nanotubes

Wang, Tao; Zhang, Yufei; Hou, Qin-Qing; Xu, Wen-Rong; Cao, Xiao‐Ping; Chow, Hak‐Fun; Kuck, Dietmar

doi:10.1021/jo302470v

Cited by 58 publications

(45 citation statements)

References 59 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The out‐out form could be reconstituted quantitatively by the introduction of xenon or helium to the aqueous solution to provide a guest molecule . Overall, it is likely that, if completely evacuated of guests, most cryptophanes will implode, unless crown‐saddle isomerisation is constricted by very short linkers or in examples in which the CTB is a tribenzotriquinacene …”

Section: Methodsmentioning

confidence: 99%

“…Dynamic covalent chemistry has been a successful approach to the synthesis of various types of organic cage . Imine‐linked cryptophanes have been previously reported by Warmuth and by Kuck, through reaction of aldehyde groups decorating the periphery of CTBs with aliphatic, cyclic, or aromatic diamines to give symmetrical capsules, with cage formation sometimes requiring the presence of a guest . This strategy can also be used to generate larger cube‐like cages with eight CTB units .…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Fully Collapsed Imploded Cryptophanes in Solution and in the Solid State

Thorp‐Greenwood

Howard

Kuhn

et al. 2019

Chemistry A European J

View full text Add to dashboard Cite

Cryptophanes with flexible linkers derived from (±)‐tris‐(4‐formyl‐phenyl)‐cyclotriguaiacylene with either bisoxydi(ethylamine) or bis(aminopropyl)ether were isolated as single crystals, the crystal structures of which showed the proposed, but previously uncharacterised, out‐in conformation, in which both cyclotriguaiacylene fragments adopt a crown conformation with one crown sitting inside the other. The usual cage‐like out‐out conformation of the cryptophanes was observed when crystals were dissolved upon heating, and the molecules collapsed back to the out‐in isomers over time. In contrast, a cryptophane also derived from (±)‐tris‐(4‐formyl‐phenyl)‐cyclotriguaiacylene but with rigid dibenzalhydrazine linkers was isolated as the more usual out‐out isomer.

show abstract

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Fully Collapsed Imploded Cryptophanes in Solution and in the Solid State

Thorp‐Greenwood

Howard

Kuhn

et al. 2019

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Monoformylation of hydrocarbon 4 using the Rieche method [11][12][13][14][15] afforded the TBTQ-2-carbaldehyde (M/P)-6 in 56 %y ield and subsequent reduction with lithium aluminum hydride gave the corresponding primary benzylic alcohol (M/P)-9 in 80 %y ield. Interestingly,k inetically controlled CAL-B-catalyzed esterification of (M/P)-9 with vinyl acetate in MTBE did not show any enantioselectivity with regard to the inherent chirality of the TBTQ framework.…”

Section: Thepolycyclicmolecularframeworkoftribenzotriquinacenementioning

confidence: 99%

Enantiomerically Pure Tribenzotriquinacenes through Stereoselective Synthesis

et al. 2015

Self Cite

View full text Add to dashboard Cite

Inherently chiral acetophenones and benzaldehydes bearing the large, bowl-shaped framework of tribenzotriquinacene (TBTQ) were synthesized in enantiomerically pure form employing enzyme catalysis. Five-step sequences involving lipase CAL-B lead to the (M)-enantiomers, (+)-2-acetyl-TBTQ (M)-5 and (+)-2-formyl-TBTQ (M)-6, whereas use of lipase PS leads to the (P)-enantiomers, (-)-2-acetyl-TBTQ (P)-5 and (-)-2-formyl-TBTQ (P)-6, with at least 99% ee in each case. The absolute configuration of these rigid 3D building blocks was determined by X-ray diffraction analysis of the ketones 5 and by comparison of their chiroptical properties with those of the aldehydes 6.

show abstract

“…[19] In yet another case the enantiomers were successfully separated through the conversion of the pair of enantiomers into diastereomers followed by several chromatographic purification steps. [20] The structure of host 7 was verified by 1 H and 13 C NMR spectroscopy, mass spectrometry and single crystal X-ray structure analysis.…”

Section: Introductionmentioning

confidence: 99%

Tribenzotriquinacene Receptors for C₆₀ Fullerene Rotors: Towards C₃ Symmetrical Chiral Stators for Unidirectionally Operating Nanoratchets

Bredenkötter

Grzywa

Alaghemandi

et al. 2014

Chemistry A European J

View full text Add to dashboard Cite

The synthesis of a stereochemically pure concave tribenzotriquinacene receptor (7) for C60 fullerene, possessing C3 point group symmetry, by threefold condensation of C2 -symmetric 1,2-diketone synthons (5) and a hexaaminotribenzotriquinacene core (6) is described. The chiral diketone was synthesized in a five-step reaction sequence starting from C2h -symmetric 2,6-di-tert-butylanthracene. The highly diastereo-discriminating Diels-Alder reaction of 2,6-di-tert-butylanthracene with fumaric acid di(-)menthyl ester, catalyzed by aluminium chloride, is the relevant stereochemistry introducing step. The structure of the fullerene receptor was verified by (1)H and (13)C NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction. VCD and ECD spectra were recorded, which were corroborated by ab initio DFT calculations, establishing the chiral nature of 7 with about 99.7 % ee, based on the ee (99.9 %) of the chiral synthon (1). The absolute configuration of 7 could thus be established as all-S [(2S,7S,16S,21S,30S,35S)-(7)]. Spectroscopic titration experiments reveal that the host forms 1:1 complexes with either pure fullerene (C60) or fullerene derivatives, such as rotor 1'-(4-nitrophenyl)-3'-(4-N,N-dimethylaminophenyl)-pyrazolino[4',5':1,2][60]fullerene (R). The complex stability constants of the complexes dissolved in CHCl3/CS2 (1:1 vol. %) are K([C60 ⊂7]) = 319(±156) M(-1) and K([R⊂7]) = 110(±50) M(-1). With molecular dynamics simulations using a first-principles parameterized force field the asymmetry of the rotational potential for [R⊂7] was shown, demonstrating the potential suitability of receptor 7 to act as a stator in a unidirectionally operating nanoratchet.

show abstract

C₃-Symmetrical Tribenzotriquinacene Derivatives: Optical Resolution through Cryptophane Synthesis and Supramolecular Self-Assembly into Nanotubes

Cited by 58 publications

References 59 publications

Fully Collapsed Imploded Cryptophanes in Solution and in the Solid State

Fully Collapsed Imploded Cryptophanes in Solution and in the Solid State

Enantiomerically Pure Tribenzotriquinacenes through Stereoselective Synthesis

Tribenzotriquinacene Receptors for C₆₀ Fullerene Rotors: Towards C₃ Symmetrical Chiral Stators for Unidirectionally Operating Nanoratchets

Contact Info

Product

Resources

About

C3-Symmetrical Tribenzotriquinacene Derivatives: Optical Resolution through Cryptophane Synthesis and Supramolecular Self-Assembly into Nanotubes

Cited by 58 publications

References 59 publications

Fully Collapsed Imploded Cryptophanes in Solution and in the Solid State

Fully Collapsed Imploded Cryptophanes in Solution and in the Solid State

Enantiomerically Pure Tribenzotriquinacenes through Stereoselective Synthesis

Tribenzotriquinacene Receptors for C60 Fullerene Rotors: Towards C3 Symmetrical Chiral Stators for Unidirectionally Operating Nanoratchets

Contact Info

Product

Resources

About

C₃-Symmetrical Tribenzotriquinacene Derivatives: Optical Resolution through Cryptophane Synthesis and Supramolecular Self-Assembly into Nanotubes

Tribenzotriquinacene Receptors for C₆₀ Fullerene Rotors: Towards C₃ Symmetrical Chiral Stators for Unidirectionally Operating Nanoratchets