Derivatization, complexation, and absolute configurational assignment of chiral primary amines: Application of exciton‐coupled circular dichroism

Zhang, Jing; Holmes, Andrea E.; Sharma, Akanksha; Brooks, Neil R.; Rarig, Randy S.; Zubieta, Jon; Canary, James W.

doi:10.1002/chir.10158

Cited by 56 publications

(52 citation statements)

References 40 publications

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“…One form of CD, known as exciton-coupled circular dichroism (ECCD), 38 has often been applied by the Canary group, 39–44 as well as others, 45–51 for similar goals. The couplets seen in ECCD have allowed for determination of ee , as well as absolute configuration, of α-amino acids, β-amino alcohols, and primary amines.…”

Section: Introductionmentioning

confidence: 99%

A Simple Method for the Determination of Enantiomeric Excess and Identity of Chiral Carboxylic Acids

et al. 2011

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The association between an achiral copper(II) host (1) and chiral carboxylate guests was studied using exciton-coupled circular dichroism (ECCD). Enantiomeric complexes were created upon binding of the enantiomers of the carboxylate guests to the host, and the sign of the resultant CD signal allowed for determination of the configuration of the studied guest. The difference in magnitudes and shapes of the CD signals, in conjunction with linear discriminant analysis (LDA), allowed for the identity of the guest to be determined successfully. A model was created for the host:guest complexes which successfully predicts the sign of the observed CD signal. Further, Taft parameters were used in the model, leading to rationalization of the observed magnitudes of the CD signals. Finally, the enantiomeric excess (ee) of unknown samples of three chiral carboxylic acid guests was determined with an average absolute error of ± 3.0%.

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Section: Introductionmentioning

confidence: 99%

A Simple Method for the Determination of Enantiomeric Excess and Identity of Chiral Carboxylic Acids

et al. 2011

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“…The introduction of two chromophores into the environment of the chiral center, which is the key problem of the exciton chirality method, has been achieved in various ways. Zhang et al 28 linked two chromophores to the amino group of the amines and then prepared the copper complexes of the chiral ligands obtained to fix their geometry. Kurtan et al 29 -31 linked achiral bidentate (diamino) carriers to the chiral amines and then complexed the resultant conjugates with an achiral pentanediol-bridged dimeric zinc porphyrin host.…”

Section: Resultsmentioning

confidence: 99%

Absorption, fluorescence, and cd spectroscopic study of chiral recognition by a binaphthyl‐derived chromogenic calixcrown host

Kubinyi¹,

Pál²,

Baranyai³

et al. 2004

Chirality

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The (R)- and (S)-enantiomers of a binaphthyl-appended calix[4]crown-6 ether with two 2,4-dinitrophenylazo chromophore units ((R)-1 and (S)-1) as chiral hosts were tested in their reactions with the enantiomers of alpha-methylbenzylamine ((R)-MBA, (S)-MBA)) and phenylglycinol ((R)-PGL, (S)-PGL) as chiral guests. The visible absorption spectra indicate a two-step process: the first is a nonenantioselective proton transfer from the host to the guest, which is followed by the enantioselective real complexation. In the visible range of the CD spectra a positive/negative band belongs to the absorption of pure (R)-1/(S)-1, and a negative/positive exciton couplet to the absorption of (R)-1-(S)-MBA/(S)-1-(R)-MBA complexes. The latter phenomenon suggests that the complexation of amines is accompanied by a chiral arrangement of the two chromophore units in the hosts. The UV fluorescence of (R)-1/(S)-1 arising from the binaphthyl moiety is quenched by K+ ions, but not by the amine guests, showing that the interaction between the binaphthyl group and the complexed amines is weak.

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“…12 The exceptional potential of chiroptical sensing with circular dichroism (CD) probes was noticed early on by Berova and Nakanishi, who published several seminal papers with broadly useful zinc porphyrin tweezer hosts. [13][14][15][16][17][18] Their outstanding work has spurred the development of a wide variety of CD sensor designs by Borhan, [19][20][21] Canary, 22,23 Anslyn, [24][25][26][27] our group, [28][29][30][31][32][33][34][35][36][37][38] and others. [39][40][41][42][43] The large majority of CD sensing assays introduced so far relies on the formation of supramolecular assemblies, metal coordination complexes, hydrogen bond adducts, or dynamic covalent chemistry (DCC).…”

Section: Introductionmentioning

confidence: 99%

Stereochemical analysis of chiral amines, diamines, and amino alcohols: Practical chiroptical sensing based on dynamic covalent chemistry

2020

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Practical chiroptical sensing with a small group of commercially available aromatic aldehydes is demonstrated. Schiff base formation between the electron‐deficient 2,4‐dinitrobenzaldehyde probe and either primary amines, diamines, or amino alcohols proceeds smoothly in chloroform at room temperature and is completed in the presence of molecular sieves within 2.5 hours. The substrate binding coincides with a distinct circular dichroism signal induction at approximately 330 nm, which can be correlated to the absolute configuration and enantiomeric composition of the analyte. The usefulness of this sensing method is highlighted with the successful sensing of 18 aliphatic and aromatic amines and amino alcohols and five examples showing quantitative %ee determination with good accuracy.

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Derivatization, complexation, and absolute configurational assignment of chiral primary amines: Application of exciton‐coupled circular dichroism

Cited by 56 publications

References 40 publications

A Simple Method for the Determination of Enantiomeric Excess and Identity of Chiral Carboxylic Acids

A Simple Method for the Determination of Enantiomeric Excess and Identity of Chiral Carboxylic Acids

Absorption, fluorescence, and cd spectroscopic study of chiral recognition by a binaphthyl‐derived chromogenic calixcrown host

Stereochemical analysis of chiral amines, diamines, and amino alcohols: Practical chiroptical sensing based on dynamic covalent chemistry

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