Quantitative chirality sensing of terpenes and terpenoids exhibiting a single double bond as the only functional group, such as α-pinene, β-pinene and camphene, or two alkene moieties like limonene, valencene, and β-caryophyllene is among the most difficult molecular recognition tasks. In this work, a fast chiroptical sensing method that accomplishes determination of the enantiomeric excess and overall amount of a large variety of terpenes and terpenoids using readily available phosphine derived late transition metal complexes is presented. The terpene coordination is complete within 10 min and coincides with spontaneous induction of strong CD signals at long wavelengths and distinct UV changes which together allow accurate and concentration quantification.
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http://dx.doi.org/10.1021/jacs.9b13910 | DOI Listing |
J Am Chem Soc
January 2025
Department of Chemistry, University of Texas at Austin, Austin 78712, Texas, United States.
Chirality
January 2025
Department of Chemistry, Shyam Lal College, University of Delhi, New Delhi, India.
Enantiomeric analysis of chiral drugs is very significant, as their enantiomers display different pharmacological or toxicological behavior towards living systems. Among these drugs, β-blockers are available as racemates, where their enantiomers display different pharmacological effects. Herein, we report enantioselective separation of two β-blockers, namely, atenolol and sotalol, using a derivatization approach.
View Article and Find Full Text PDFSci Bull (Beijing)
December 2024
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, China. Electronic address:
Divergent synthesis of valuable molecules through common starting materials and metal catalysis represents a longstanding challenge and a significant research goal. We here describe chemodivergent, highly enantio- and regioselective nickel-catalyzed reductive and dehydrogenative coupling reactions of alkynes, aldehydes, and silanes. A single chiral Ni-based catalyst is leveraged to directly prepare three distinct enantioenriched products (silyl-protected trisubstituted chiral allylic alcohols, oxasilacyclopentenes, and silicon-stereogenic oxasilacyclopentenes) in a single chemical operation.
View Article and Find Full Text PDFJ Mol Model
January 2025
Laboratorio de Química Teórica Computacional (QTC), Facultad de Química y de Farmacia, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, 7820436, Santiago de Chile, Chile.
Context: Dopamine -monooxygenase (D M) is an essential enzyme in the organism that regioselectively converts dopamine into R-norepinephrine, the key step of the reaction, studied in this paper, is a hydrogen atom transfer (HAT) from dopamine to a superoxo complex on D M, forming a hydroperoxo intermediate and dopamine radical. It was found that the formation of a hydrogen bond between dopamine and the D M catalyst strengthens the substrate-enzyme interaction and facilitates the HAT which takes place selectively to give the desired enantiomeric form of the product. Six reactions leading to the hydroperoxo intermediate were analyzed in detail using theoretical and computational tools in order to identify the most probable reaction mechanism.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
Institut de Química Computacional i Catàlisi (IQCC), Universitat de Girona, Maria Aurèlia Capmany 69, 17003 Girona, Spain.
Discrimination of enantiomeric substrate molecules is one of the fundamental properties of biological hosts. Replicating enantioselective molecular recognition with synthetic receptors is a topic of interest with implications in diverse applications such as bioinspired enantioselective catalysis, enantiomer separation, or sensing. In this review, five different systems reported in the literature are discussed, and their performance and versatility are analyzed.
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