O and alkenes are important reactants in the formation of SOA in the atmosphere. The intermediates and reaction mechanism of ozonation of alkene is an important topic in atmospheric chemistry. In this study, the low-temperature matrix isolation was used to capture the intermediates such as Primary ozonides (POZs), Criegee Intermediates (CIs), and Secondary ozonides (SOZs) generated from ozonation of 2-methyl-1-butene (2M1B) and 2-methyl-2-butene (2M2B). The results have been identified by the vacuum infrared spectroscopy and theoretical calculation. Our results show that during the ozonation of asymmetric alkenes, two kinds of CIs and more than two kinds of SOZs were generated due to the different decomposition modes of POZs. The infrared absorption peaks of (CH)COO and CHCHC(CH)OO for O-O telescopic vibration was determined to be 889 cm and 913 cm, respectively. Using the merged jet method, it was found that a large amount of HCHO was produced during the ozonation of 2M1B, and glyoxal and methylglyoxal were produced in the ozonation of 2M2B. Our findings highlight the importance of asymmetric alkene ozonolysis reactions in producing CIs, further improving the understanding of the generation of CIs from ozonation of alkenes.
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http://dx.doi.org/10.1016/j.chemosphere.2020.126413 | DOI Listing |
RSC Chem Biol
January 2025
Department of Chemistry, Emory University Atlanta GA 30322 USA
Members of the old yellow enzyme (OYE) family utilize a flavin mononucleotide cofactor to catalyze the asymmetric reduction of activated alkenes. The 2-enoate reductase (2-ER) subfamily are of particular industrial relevance as they can reduce α/β alkenes near electron-withdrawing groups. While the broader OYE family is being extensively explored for biocatalytic applications, oxygen sensitivity and poor expression yields associated with the presence of an Fe/S cluster in 2-ERs have hampered their characterization.
View Article and Find Full Text PDFACS Cent Sci
January 2025
Department of Chemistry, Zhejiang University, Hangzhou 310058, China.
Recently, nickel catalysts have garnered considerable attention for their efficacy and versatility in asymmetric catalysis, attributed to their distinctive properties. However, the use of cost-effective and sustainable divalent nickel catalysts in C-H activation/asymmetric alkene insertion poses significant challenges due to the intricate control of stereochemistry in the transformation of the tetracoordinate C-Ni(II) intermediate. Herein, we report a Ni(II)-catalyzed enantioselective C-H/N-H annulation with oxabicyclic alkenes.
View Article and Find Full Text PDFACS Cent Sci
January 2025
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.
Multicomponent reactions (MCRs), highly sought-after methods to produce atom-, step-, and energy-economic organic syntheses, have been developed extensively. However, catalytic asymmetric MCRs, especially those involving radical species, remain largely unexplored owing to the difficulty in stereoselectively regulating the extraordinarily high reactivity of open-shell radical species. Herein, we report a conceptually novel catalytic asymmetric three-component radical cascade reaction of readily accessible glycine esters, α-bromo carbonyl compounds and 2-vinylcyclopropyl ketones via synergistic photoredox/Brønsted acid catalysis, in which three sequential C-C (σ/π/σ) bond-forming events occurred through a radical addition/ring-opening/radical-radical coupling protocol, affording an array of valuable enantioenriched unnatural α-amino acid derivatives bearing two contiguous stereogenic centers and an alkene moiety in moderate to good yield with high diastereoselectivity, excellent enantioselectivity and good -dominated geometry under mild reaction conditions.
View Article and Find Full Text PDFDalton Trans
January 2025
Chongqing Key Laboratory of Green Catalysis Materials and Technology, College of Chemistry, Chongqing Normal University, Chongqing 401331, China.
A deeper understanding of the mechanisms underlying transition metal-catalyzed transformation is crucial for developing innovative strategies to synthesize chiral organoselenium compounds. In this study, we developed and investigated a three-layer chirality relay model for the rhodium-catalyzed asymmetric hydroselenation of alkenes through density functional theory (DFT) calculations. In the back layer of this model, the four bulky substituents on the phosphorus atom of the bidentate chiral MeO-BIPHEP ligand were positioned on axial and equatorial bonds, thereby influencing the configuration of the middle layer.
View Article and Find Full Text PDFAcc Chem Res
January 2025
Shenzhen Grubbs Institute and Department of Chemistry, Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, Guangdong 518055, China.
ConspectusChiral organosilicon compounds bearing a Si-stereogenic center have attracted increasing attention in various scientific communities and appear to be a topic of high current relevance in modern organic chemistry, given their versatile utility as chiral building blocks, chiral reagents, chiral auxiliaries, and chiral catalysts. Historically, access to these non-natural Si-stereogenic silanes mainly relies on resolution, whereas their asymmetric synthetic methods dramatically lagged compared to their carbon counterparts. Over the past two decades, transition-metal-catalyzed desymmetrization of prochiral organosilanes has emerged as an effective tool for the synthesis of enantioenriched Si-stereogenic silanes.
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