Absolute Configuration and Conformational Analysis of Chiral Compounds via Experimental and Theoretical Prediction of Chiroptical Properties: ORD, ECD, and VCD

Petrovic, Ana G.; Berova, Nina; Alonso‐Gómez, José Lorenzo

doi:10.1002/9783527664610.ch3

Cited by 14 publications

(20 citation statements)

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“…It is commonly accepted that chirality, an amplifier of molecular diversity, has triggered evolution in nature by rendering most physiological interactions regio- and stereospecific [ 13 , 14 ]. Bioactive secondary metabolites are principally chiral compounds, necessitating the unambiguous determination of their absolute configuration (AC) and conformations, in order to gain insights into their mode of action or biosynthetic origin [ 14 , 15 ].…”

Section: Introductionmentioning

confidence: 99%

Bifurcatriol, a New Antiprotozoal Acyclic Diterpene from the Brown Alga Bifurcaria bifurcata

et al. 2017

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Linear diterpenes that are commonly found in brown algae are of high chemotaxonomic and ecological importance. This study reports bifurcatriol (1), a new linear diterpene featuring two stereogenic centers isolated from the Irish brown alga Bifurcaria bifurcata. The gross structure of this new natural product was elucidated based on its spectroscopic data (IR, 1D and 2D-NMR, HRMS). Its absolute configuration was identified by experimental and computational vibrational circular dichroism (VCD) spectroscopy, combined with the calculation of 13C-NMR chemical shielding constants. Bifurcatriol (1) was tested for in vitro antiprotozoal activity towards a small panel of parasites (Plasmodium falciparum, Trypanosoma brucei rhodesiense, T. cruzi, and Leishmania donovani) and cytotoxicity against mammalian primary cells. The highest activity was exerted against the malaria parasite P. falciparum (IC50 value 0.65 μg/mL) with low cytotoxicity (IC50 value 56.6 μg/mL). To our knowledge, this is the first successful application of VCD and DP4 probability analysis of the calculated 13C-NMR chemical shifts for the simultaneous assignment of the absolute configuration of multiple stereogenic centers in a long-chain acyclic natural product.

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Section: Introductionmentioning

confidence: 99%

Bifurcatriol, a New Antiprotozoal Acyclic Diterpene from the Brown Alga Bifurcaria bifurcata

et al. 2017

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“…The absolute stereochemistry of the enantiomers was assigned by directly comparing the experimental ECD spectrum acquired online during the HPLC separation with the computed ECD spectrum of an arbitrarily chosen enantiomer. Such stereochemical analysis of chiral compounds, that is, by combining online HPLC‐ECD analysis and quantum chemical calculations has already proven to be substantially useful, efficient, and reliable for stereochemical studies of various chiral organic molecules , …”

Section: Resultsmentioning

confidence: 99%

“…Such stereochemical analysis of chiral compounds, that is, by combining online HPLC-ECD analysis and quantum chemical calculations has already proven to be substantially useful, efficient, and reliable for stereochemical studies of various chiral organic molecules. [10,[16][17][18][19][20] The ECD chromatogram of 10, which was recorded at 280 nm, has two peaks with opposite signs (Figure 4A, bottom). However, there are three peaks in the photodiode array (PDA) chromatogram, which indicates that the first eluted compound cannot be detected by ECD ( Figure 4A, top).…”

Section: Resultsmentioning

confidence: 99%

Atropoisomerism in Mono‐ and Diaryl‐Substituted 4‐Amino‐2,6‐lutidines

et al. 2016

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The Suzuki–Miyaura reaction of 4‐amino‐3,5‐dibromo‐2,6‐lutidine with various ortho‐substituted phenylboronic acids resulted in the formation of a series of mono‐ and diarylated lutidines in the form of atropisomers. The absolute stereochemistry of the chiral compounds was established, in some cases, by X‐ray crystal structure analysis and HPLC‐ECD (ECD = electronic circular dichroism) in combination with time‐dependent density functional theory (TDDFT) calculations.

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“…The outcome of birefringence is the rotation of the plane polarized wave when traveling through a chiral system, commonly known as optical rotation. While originally these measurements were performed only at 589 nm, the D-line of sodium, resulting in the α D values characteristic of any chiral molecule, later on, the measurement of the optical rotation at different wavelengths provided optical rotatory dispersion (ORD), a more reliable methodology for structural elucidation [5,6]. On the other hand, CD can be measured in the infrared region, as is the case for vibrational CD (VCD), or in the ultra violet visible region of the spectrum, with spectroscopies such as electronic CD (ECD), circularly polarized luminescence, or Raman optical activity [7].…”

Section: Introductionmentioning

confidence: 99%

Chiroptical Sensing: A Conceptual Introduction

Ozcelik

Ulrih

Petrovic

et al. 2020

Sensors

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Chiroptical responses have been an essential tool over the last decades for chemical structural elucidation due to their exceptional sensitivity to geometry and intermolecular interactions. In recent times, there has been an increasing interest in the search for more efficient sensing by the rational design of tailored chiroptical systems. In this review article, advances made in chiroptical systems towards their implementation in sensing applications are summarized. Strategies to generate chiroptical responses are illustrated. Theoretical approaches to assist in the design of these systems are discussed. The development of efficient chiroptical reporters in different states of matter, essential for the implementation in sensing devises, is reviewed. In the last part, remarkable examples of chiroptical sensing applications are highlighted.

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Absolute Configuration and Conformational Analysis of Chiral Compounds via Experimental and Theoretical Prediction of Chiroptical Properties: ORD, ECD, and VCD

Cited by 14 publications

References 55 publications

Bifurcatriol, a New Antiprotozoal Acyclic Diterpene from the Brown Alga Bifurcaria bifurcata

Bifurcatriol, a New Antiprotozoal Acyclic Diterpene from the Brown Alga Bifurcaria bifurcata

Atropoisomerism in Mono‐ and Diaryl‐Substituted 4‐Amino‐2,6‐lutidines

Chiroptical Sensing: A Conceptual Introduction

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