Intramolecular Interactions of Trityl Groups

Ściebura, Jacek; Janiak, Agnieszka; Stasiowska, Agata; Grajewski, Jakub; Gawrońska, K.; Rychłewska, Urszula; Gawroński, Jacek

doi:10.1002/cphc.201301204

Cited by 14 publications

(15 citation statements)

References 36 publications

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“…6 Meanwhile, introduction of an amide linker between the inductor and the receptor caused a signicant increase of this distance, which resulted in consequent lack of involvement of the two reporter units in mutual steric interactions. For ditrityl ethers and amines the structural feature that served to identify mutual interactions of the trityl groups was their conformationthe trityls that were not involved in steric interactions had an approximate C 3 -symmety.…”

Section: Discussionmentioning

confidence: 99%

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Double helicity induction in chiral bis(triphenylacetamides)

et al. 2015

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A combination of experimental methods (ECD, X-ray diffraction) and theoretical calculations allowed the description of chirality transfer in bis(triphenylacetamides). For the first time it has been shown that effective helicity induction in a trityl chromophore is not only due to the presence of stereogenic center(s) but is also caused by other chirality inductors such as an axis of chirality. For all experimental and computed ECD spectra a uniformly identical sequence of signs of the Cotton effects has been found: negative at around 215 nm and positive below 200 nm. This result can only be explained by the dependence of the ECD spectra on the R absolute configuration of the proximal stereogenic element. The chirality transfer is achieved through a series of weak intramolecular interactions. Helicities of the trityl chromophores and their propeller shapes are influenced by the structure of the chiral inductor and the steric hindrance at amide nitrogen atoms. The stereogenic centers in the diamide unit act independently as chirality inductors and the direct trityl/trityl interactions are only rarely observed.Characteristic for the investigated crystals is the complete hindrance of the amide NH groups and their inability to be involved in any intermolecular interactions as well as their highly restricted ability for the formation of intramolecular hydrogen bonds. This results from the presence of Tr groups, which act as supramolecular NH protecting groups, especially when attached to the rigid carbocycles.

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Section: Discussionmentioning

confidence: 99%

“…Fig. 6 Only in the case of amide 6 the number of the individual low-energy structures exceeded seven. Computationally found number of thermally accessible conformers was lower than reported previously for N,N 0 -ditrityldiamines or O,O 0 -ditrityldiols.…”

Section: Molecular Structure In Silico and In Crystalmentioning

confidence: 91%

Double helicity induction in chiral bis(triphenylacetamides)

et al. 2015

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“…Thus, the conformation of the chromophore reflects not only the chiral neighborhood created by stereogenic centers, buta lso the chromophores mustm atch each other.T his situation is characteristicf or molecular propellers such as 1,2-ditrityl derivatives of chiral, nonracemic vicinal diols and diamines. [36] From those findings, the following questions emerged.F irst, what is the origin of the opticala ctivity of the benzhydryl ethers in this study?S econd, are the observed Cotton effects the results of interactions within the isolated chromophore or interactions between chromophores?I no ther words, can we expect exciton coupling between the neighboring benzhydryl groups?T hird, is there any regularity that associates the structure of the chromophorew ith the generated rotatory strengthsresponsible for the observed Cotton effect?…”

Section: Electroniccircular Dichroism Studymentioning

confidence: 99%

“…Of particulari nterest are the chiropticalp roperties of derived benzhydryl ethers attached to achiral molecule. [18] Trityl derivatives of chiral alcohols [19] or chiral amines [20] are alternatives for chromophoric derivatization but they are more difficult to prepare and are less stable. An assembly of ap olar substrate and an onpolar reporting chromophorecan be as ource of valuable The benzhydryl (diphenylmethyl) group is am olecular propeller that can act as ac hirality reporteri fi ti si ntroduced nearby as tereogenic center by making an ether bond.…”

Section: Introductionmentioning

confidence: 99%

Benzhydryl Ethers of Tartaric Acid Derivatives: Stereochemical Response of a Dynamically Chiral Propeller

et al. 2017

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The benzhydryl (diphenylmethyl) group is a molecular propeller that can act as a chirality reporter if it is introduced nearby a stereogenic center by making an ether bond. The hydrophobic character of the benzhydryl group allows transformation of insoluble natural tartaric acid derivatives into soluble entities in a nonpolar environment. Electronic circular dichroism spectra, recorded within the short-wavelength region of the phenyl B transitions (190-200 nm) shows strong bisignate Cotton effects. The signs and magnitudes of these Cotton effects are a function of absolute configuration and conformation of the molecule and do not primarily arise from exciton coupling of chiral benzhydryl chromophores. In crystals, the main-chain conformation is stabilized by intramolecular hydrogen bonds and CH-CO dipolar interactions. The number of the donor NH groups has a pronounced effect on the preferred conformations and inclusion properties of benzhydryl-(R,R)-tartaric acid diamides. Evidence is shown for the solvent dependency of the conformations of NH amides of tartaric acid diphenylmethyl ethers.

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“…Recently, the usability of the trityl group has been expanded on catalysis and medicinal chemistry [45,46,47]. We and others have shown that the stereodynamic propeller-like trityl group, characterized by P - or M -helicity (i.e., has the sense of a twist of the phenyl groups) [48,49,50,51,52,53,54], when attached to the permanently chiral inducer can act as a chirality reporter adapting its structure to the chiral environment [46].…”

Section: Introductionmentioning

confidence: 99%

Chiral Cocrystal Solid Solutions, Molecular Complexes, and Salts of N-Triphenylacetyl-l-Tyrosine and Diamines

Czapik

Jelecki

Kwit

2019

IJMS

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The molecular recognition process and the ability to form multicomponent supramolecular systems have been investigated for the amide of triphenylacetic acid and l-tyrosine (N-triphenylacetyl-l-tyrosine, TrCOTyr). The presence of several supramolecular synthons within the same amide molecule allows the formation of various multicomponent crystals, where TrCOTyr serves as a chiral host. Isostructural crystals of solvates with methanol and ethanol and a series of binary crystalline molecular complexes with selected organic diamines (1,5-naphthyridine, quinoxaline, 4,4′-bipyridyl, and DABCO) were obtained. The structures of the crystals were planned based on non-covalent interactions (O–H···N or N–H+···O− hydrogen bonds) present in a basic structural motif, which is a heterotrimeric building block consisting of two molecules of the host and one molecule of the guest. The complex of TrCOTyr with DABCO is an exception. The anionic dimers built off the TrCOTyr molecules form a supramolecular gutter, with trityl groups located on the edge and filled by DABCO cationic dimers. Whereas most of the racemic mixtures crystallize as racemic crystals or as conglomerates, the additional tests carried out for racemic N-triphenylacetyl-tyrosine (rac-TrCOTyr) showed that the compound crystallizes as a solid solution of enantiomers.

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Intramolecular Interactions of Trityl Groups

Cited by 14 publications

References 36 publications

Double helicity induction in chiral bis(triphenylacetamides)

Double helicity induction in chiral bis(triphenylacetamides)

Benzhydryl Ethers of Tartaric Acid Derivatives: Stereochemical Response of a Dynamically Chiral Propeller

Chiral Cocrystal Solid Solutions, Molecular Complexes, and Salts of N-Triphenylacetyl-l-Tyrosine and Diamines

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