Optically Active Trialkynyl(phenyl)methane: Synthesis and Determination of Its Absolute Configuration by Vibrational Circular Dichroism (VCD) and Optical Rotatory Dispersion (ORD)

Buschhaus, Boris; Convertino, Vito; Rivera‐Fuentes, Pablo; Alonso‐Gómez, José Lorenzo; Petrovic, Ana G.; Diederich, François

doi:10.1002/ejoc.201000076

Cited by 6 publications

(3 citation statements)

References 20 publications

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“…A large variety of structural types have been examined, including epoxides and cyclopropanes, [55][56][57][58] bicyclic and tricyclic structures, [59][60][61][62][63][64][65][66][67] chiral structures with no chiral center (atropisomer or molecules with axial or helical chirality), [68][69][70][71][72][73][74][75][76][77][78][79][80][81][82][83] sulfur or phosphorus containing compounds, 77,[84][85][86][87][88] flexible molecules, 56,[89][90][91] and other structures that do not fit into any of the above categories. [92][93][94][95][96][97] The following examples highlight the versatility of VCD as a powerful tool for the AC determinations of different types of chiral organic structures.…”

Section: Determination Of Absolute Configuration Of Small Organic Molmentioning

confidence: 99%

Determination of Absolute Configuration of Chiral Molecules Using Vibrational Optical Activity: A Review

Wang²,

Dukor³

et al. 2011

Appl Spectrosc

289

218

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Determination of the absolute handedness, known as absolute configuration (AC), of chiral molecules is an important step in any field related to chirality, especially in the pharmaceutical industry. Vibrational optical activity (VOA) has become a powerful tool for the determination of the AC of chiral molecules in the solution state after nearly forty years of evolution. VOA offers a novel alternative, or supplement, to X-ray crystallography, permitting AC determinations on neat liquid, oil, and solution samples without the need to grow single crystals of the pure chiral sample molecules as required for X-ray analysis. By comparing the sign and intensity of the measured VOA spectrum with the corresponding ab initio density functional theory (DFT) calculated VOA spectrum of a chosen configuration, one can unambiguously assign the AC of a chiral molecule. Comparing measured VOA spectra with calculated VOA spectra of all the conformers can also provide solution-state conformational populations. VOA consists of infrared vibrational circular dichroism (VCD) and vibrational Raman optical activity (ROA). Currently, VCD is used routinely by researchers in a variety of backgrounds, including molecular chirality, asymmetric synthesis, chiral catalysis, drug screening, pharmacology, and natural products. Although the application of ROA in AC determination lags behind that of VCD, with the recent implementation of ROA subroutines in commercial quantum chemistry software, ROA will in the future complement VCD for AC determination. In this review, the basic principles of the application of VCD to the determination of absolute configuration in chiral molecules are described. The steps required for VCD spectral measurement and calculation are outlined, followed by brief descriptions of recently published papers reporting the determination of AC in small organic, pharmaceutical, and natural product molecules.

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Section: Determination Of Absolute Configuration Of Small Organic Molmentioning

confidence: 99%

Determination of Absolute Configuration of Chiral Molecules Using Vibrational Optical Activity: A Review

Wang²,

Dukor³

et al. 2011

Appl Spectrosc

289

218

View full text Add to dashboard Cite

show abstract

“…That said, we note that a series of technical challenges must be addressed, as elaborated in a number of publications ( Petrovic et al, 2015 ; Collins et al, 2017 ; Krupová et al, 2020 ), to further increase the detection sensitivity, acquisition speed, and spectral resolution. In many recent investigations, multimodal spectroscopic techniques have also been used to extract complementary details and/or cross validate the results ( Buschhaus et al, 2010 ; Rivera-Fuentes et al, 2010 ; Duan et al, 2015b ).…”

Section: Discussionmentioning

confidence: 99%

Polarimetric Measurements of Surface Chirality Based on Linear and Nonlinear Light Scattering

2021

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A molecule, molecular aggregate, or protein that cannot be superimposed on its mirror image presents chirality. Most living systems are organized by chiral building blocks, such as amino acids, peptides, and carbohydrates, and any change in their molecular structure (i.e., handedness or helicity) alters the biochemical and pharmacological functions of the molecules, many of which take place at surfaces. Therefore, studying surface chirogenesis at the nanoscale is fundamentally important and derives various applications. For example, since proteins contain highly ordered secondary structures, the intrinsic chirality can be served as a signature to measure the dynamics of protein adsorption and protein conformational changes at biological surfaces. Furthermore, a better understanding of chiral recognition and separation at bio-nanointerfaces is helpful to standardize chiral drugs and monitor the synthesis of adsorbents with high precision. Thus, exploring the changes in surface chirality with polarized excitations would provide structural and biochemical information of the adsorbed molecules, which has led to the development of label-free and noninvasive measurement tools based on linear and nonlinear optical effects. In this review, the principles and selected applications of linear and nonlinear optical methods for quantifying surface chirality are introduced and compared, aiming to conceptualize new ideas to address critical issues in surface biochemistry.

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“…Tertiary chiral diynes are important building blocks that could be used in a broad array of reactivities and transformed into more complex compounds . Diederich has proven the utility of 1,4-diynes as precursors of chiral oligomers, two- and three-dimensional alleno-acetylenic chiral macrocycles . Chauvin and co-workers have described the synthesis of carbo-benzene from 1,4-dialkynylbutatrienes .…”

mentioning

confidence: 99%

Synthesis of Enantiopure Tertiary Skipped Diynes via One-Pot Desymmetrizing TMS-Cleavage

Nechab

Vanthuyne

2012

Org. Lett.

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Optically Active Trialkynyl(phenyl)methane: Synthesis and Determination of Its Absolute Configuration by Vibrational Circular Dichroism (VCD) and Optical Rotatory Dispersion (ORD)

Cited by 6 publications

References 20 publications

Determination of Absolute Configuration of Chiral Molecules Using Vibrational Optical Activity: A Review

Determination of Absolute Configuration of Chiral Molecules Using Vibrational Optical Activity: A Review

Polarimetric Measurements of Surface Chirality Based on Linear and Nonlinear Light Scattering

Synthesis of Enantiopure Tertiary Skipped Diynes via One-Pot Desymmetrizing TMS-Cleavage

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