{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T00:56:29Z","timestamp":1760057789212,"version":"build-2065373602"},"reference-count":81,"publisher":"MDPI AG","issue":"5","license":[{"start":{"date-parts":[[2025,2,28]],"date-time":"2025-02-28T00:00:00Z","timestamp":1740700800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22401072","B2022208024","B2023208015"],"award-info":[{"award-number":["22401072","B2022208024","B2023208015"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100003787","name":"Natural Science Foundation of Hebei Province","doi-asserted-by":"publisher","award":["22401072","B2022208024","B2023208015"],"award-info":[{"award-number":["22401072","B2022208024","B2023208015"]}],"id":[{"id":"10.13039\/501100003787","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>A facile strategy to increase the chemoselectivity of domino reactions was proposed and successfully applied in the \u03b1-functionalization of ketones. The strategy involved widening the activation energy of the main reaction and side reaction through intermolecular interactions, thereby increasing the chemoselectivity of the domino reaction. In the proposed \u03b1-functionalization reaction, TMSCF3 acted as an excellent reagent which increased the nucleophilicity of DMF through the Van der Waals force and reduced the nucleophilicity of H2O through a hydrogen bond. We found that TMSCF3 can increase the activation energy difference between the main reaction and side reaction using DFT calculations, which greatly increased chemoselectivity and avoided the formation of by-products. TMSCF3 was recycled by rectification, and the average recovery rate was 87.2%. DFT calculations, XRD experiments, and control experiments were performed to support this mechanism. We are confident that this strategy has the potential to deliver significant practical advancements while simultaneously fostering broader innovation in the field of domino synthesis.<\/jats:p>","DOI":"10.3390\/molecules30051114","type":"journal-article","created":{"date-parts":[[2025,2,28]],"date-time":"2025-02-28T06:45:42Z","timestamp":1740725142000},"page":"1114","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Computational and Experimental Studies on the \u03b1-Functionalization of Ketones Using Domino Reactions: A Strategy to Increase Chemoselectivity at the \u03b1-Carbon of Ketones"],"prefix":"10.3390","volume":"30","author":[{"given":"Hui","family":"Sun","sequence":"first","affiliation":[{"name":"Manganese Catalysis and Asymmetric Synthesis Laboratory, Hebei University of Science and Technology, Shijiazhuang 050018, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Li-Heng","family":"Yang","sequence":"additional","affiliation":[{"name":"Manganese Catalysis and Asymmetric Synthesis Laboratory, Hebei University of Science and Technology, Shijiazhuang 050018, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Meng-Yun","family":"Fu","sequence":"additional","affiliation":[{"name":"Manganese Catalysis and Asymmetric Synthesis Laboratory, Hebei University of Science and Technology, Shijiazhuang 050018, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Bin","family":"Cui","sequence":"additional","affiliation":[{"name":"Manganese Catalysis and Asymmetric Synthesis Laboratory, Hebei University of Science and Technology, Shijiazhuang 050018, China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2025,2,28]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"115","DOI":"10.1021\/cr950027e","article-title":"Domino reactions in organic synthesis","volume":"96","author":"Tietze","year":"1996","journal-title":"Chem. Rev."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"7134","DOI":"10.1002\/anie.200601872","article-title":"Cascade reactions in total synthesis","volume":"45","author":"Nicolaou","year":"2006","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"167","DOI":"10.1038\/nchem.539","article-title":"Organocatalytic cascade reactions as a new tool in total synthesis","volume":"2","author":"Grondal","year":"2010","journal-title":"Nat. Chem."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"2390","DOI":"10.1021\/cr400215u","article-title":"Catalytic C\u2013C bond-forming multi-component cascade or domino reactions: Pushing the boundaries of complexity in asymmetric organocatalysis","volume":"114","author":"Volla","year":"2014","journal-title":"Chem. Rev."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1557","DOI":"10.1039\/C5CS00105F","article-title":"Cascade polycyclizations in natural product synthesis","volume":"45","author":"Ardkhean","year":"2016","journal-title":"Chem. Soc. Rev."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"2809","DOI":"10.1021\/acs.accounts.7b00406","article-title":"Achieving Molecular Complexity via Stereoselective Multiple Domino Reactions Promoted by a Secondary Amine Organocatalyst","volume":"50","author":"Chauhan","year":"2017","journal-title":"Acc. Chem. Res."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"3968","DOI":"10.1039\/D1QO00269D","article-title":"Recent advances of chromone-based reactants in the catalytic asymmetric domino annulation reaction","volume":"8","author":"Zhang","year":"2021","journal-title":"Org. Chem. Front."},{"key":"ref_8","first-page":"60","article-title":"Masafumi Ueda, Umpolung reactions at the \u03b1-carbon position of carbonyl compounds","volume":"2013","year":"2013","journal-title":"ARKIVOC"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"5466","DOI":"10.1021\/acscatal.8b01263","article-title":"Catalytic asymmetric oxidative enamine transformations","volume":"8","author":"Zhu","year":"2018","journal-title":"ACS Catal."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"8778","DOI":"10.1021\/jacs.9b04325","article-title":"\u03b1-Functionalization of cyclic secondary amines: Lewis acid promoted addition of organometallics to transient imines","volume":"141","author":"Paul","year":"2019","journal-title":"J. Am. Chem. Soc."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"1994","DOI":"10.1021\/acs.orglett.3c00647","article-title":"\u03b1-Amino radical-mediated difunctionalization of alkenes with polyhaloalkanes and N-heteroarenes","volume":"25","author":"Shen","year":"2023","journal-title":"Org. Lett."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"795","DOI":"10.1021\/acs.accounts.4c00009","article-title":"Reductive functionalization of pyridine-fused N-heteroarenes","volume":"57","author":"Jia","year":"2024","journal-title":"Acc. Chem. Res."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"3653","DOI":"10.1002\/adsc.202400720","article-title":"Electrochemical \u03b1-functionalization of N-aryl-activated tertiary amines","volume":"366","author":"Wang","year":"2024","journal-title":"Adv. Synth. Catal."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"793","DOI":"10.3390\/81100793","article-title":"The chemistry of \u03b1-haloketones and their utility in heterocyclic synthesis","volume":"8","author":"Erian","year":"2003","journal-title":"Molecules"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"16074","DOI":"10.1021\/ja4096472","article-title":"Simple catalytic mechanism for the direct coupling of \u03b1-carbonyls with functionalized amines: A one-step synthesis of plavix","volume":"135","author":"Evans","year":"2013","journal-title":"J. Am. Chem. Soc."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"4372","DOI":"10.1039\/C4CC09524C","article-title":"Copper-catalyzed direct \u03b1-ketoesterification of propiophenones with acetophenones via C(sp3)\u2013H oxidative cross-coupling","volume":"51","author":"Du","year":"2015","journal-title":"Chem. Commun."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"406","DOI":"10.1021\/ol503683q","article-title":"A versatile and one-pot strategy to synthesize \u03b1-amino ketones from benzylic secondary alcohols using N-bromosuccinimide","volume":"17","author":"Guha","year":"2015","journal-title":"Org. Lett."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"11565","DOI":"10.1021\/acs.joc.6b01595","article-title":"Electrochemically oxidative \u03b1-C\u2013H functionalization of ketones: A cascade synthesis of \u03b1-amino ketones mediated by NH4I","volume":"81","author":"Liang","year":"2016","journal-title":"J. Org. Chem."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"6754","DOI":"10.1021\/acssuschemeng.6b01718","article-title":"Practical approach for quantitative green esterifications","volume":"4","author":"Liu","year":"2016","journal-title":"ACS Sust. Chem. Eng."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"20394","DOI":"10.1039\/C7RA02298K","article-title":"I2\/TBHP-mediated oxidative coupling of ketones and toluene derivatives: A facile method for the preparation of \u03b1-benzoyloxy ketones","volume":"7","author":"Chen","year":"2017","journal-title":"RSC Adv."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"1079","DOI":"10.3762\/bjoc.13.107","article-title":"\u03b1-Acetoxyarone synthesis via iodine-catalyzed and tert-butyl hydroperoxide-mediateded self-intermolecular oxidative coupling of aryl ketones","volume":"13","author":"Tan","year":"2017","journal-title":"Beilstein J. Org. Chem."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"111058","DOI":"10.1016\/j.mcat.2020.111058","article-title":"\u03b1-Amination reaction of different ketones mediated by carbohydrate Cu2+ complexes","volume":"493","author":"Rossi","year":"2020","journal-title":"Mol. Catal."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"12333","DOI":"10.1002\/slct.201903028","article-title":"Iodine-mediated nucleophilic direct oxidative \u03b1-acetoxylation and \u03b1-alkoxylation of ketones","volume":"4","author":"Pogaku","year":"2019","journal-title":"ChemistrySelect"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"e202300061","DOI":"10.1002\/tcr.202300061","article-title":"Organocatalytic Synthesis of chiral halogenated compounds","volume":"23","author":"Shibatomi","year":"2023","journal-title":"Chem. Rec."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"517","DOI":"10.1055\/s-0030-1258328","article-title":"\u03b1-Functionalization of carbonyl compounds using hypervalent iodine reagents","volume":"2011","author":"Merritt","year":"2011","journal-title":"Synthesis"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"4278","DOI":"10.1039\/c4ob00318g","article-title":"Hypervalent iodine: A powerful electrophile for asymmetric \u03b1-functionalization of carbonyl compounds","volume":"12","author":"Dong","year":"2014","journal-title":"Org. Biomol. Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"3328","DOI":"10.1021\/acs.chemrev.5b00547","article-title":"Advances in synthetic applications of hypervalent iodine compounds","volume":"116","author":"Yoshimura","year":"2016","journal-title":"Chem. Rev."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"2599","DOI":"10.1002\/anie.201610274","article-title":"Enolonium species\u2014Umpoled enolates","volume":"56","author":"Arava","year":"2017","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"3212","DOI":"10.1021\/acs.accounts.8b00468","article-title":"Cyclic hypervalent iodine reagents: Enabling tools for bond disconnection via reactivity umpolung","volume":"51","author":"Hari","year":"2018","journal-title":"Acc. Chem. Res."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"17856","DOI":"10.1002\/anie.201911793","article-title":"Umpolung strategy for \u03b1-functionalization of aldehydes for the addition of thiols and other nucleophiles","volume":"58","author":"Blom","year":"2019","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"3976","DOI":"10.1039\/C4CC00402G","article-title":"A copper-catalyzed formal O\u2013H insertion reaction of \u03b1-diazo-1,3-dicarbonyl compounds to carboxylic acids with the assistance of isocyanide","volume":"50","author":"Wang","year":"2014","journal-title":"Chem. Commun."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"6930","DOI":"10.1021\/acscatal.6b02184","article-title":"Asymmetric catalytic insertion of \u03b1-diazo carbonyl compounds into O\u2013H bonds of carboxylic acids","volume":"6","author":"Tan","year":"2016","journal-title":"ACS Catal."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"8410","DOI":"10.1002\/anie.201602137","article-title":"Rhodium-catalyzed geminal oxyfluorination and oxytrifluoro-methylation of diazocarbonyl compounds","volume":"55","author":"Yuan","year":"2016","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"3078","DOI":"10.1021\/acs.orglett.6b01189","article-title":"Catalytic oxidative carbene coupling of \u03b1-diazo carbonyls for the synthesis of \u03b2-amino ketones via C(sp3)\u2013H functionalization","volume":"18","author":"Zhang","year":"2016","journal-title":"Org. Lett."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"928","DOI":"10.1002\/anie.201004374","article-title":"Nucleophilic \u03b1-arylation and \u03b1-alkylation of ketones by polarity inversion of N-alkoxyenamines: Entry to the umpolung reaction at the \u03b1-carbon position of carbonyl compounds","volume":"50","author":"Miyoshi","year":"2011","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"10373","DOI":"10.1039\/C6CC04638J","article-title":"Copper-catalyzed oxyamination of electron-deficient alkenes with N-acyloxyamines","volume":"52","author":"Ren","year":"2016","journal-title":"Chem. Commun."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"5515","DOI":"10.1021\/jacs.6b02533","article-title":"One-pot synthesis of benzene-fused medium-ring ketones: Gold catalysis-enabled enolate umpolung reactivity","volume":"138","author":"Xu","year":"2016","journal-title":"J. Am. Chem. Soc."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"6768","DOI":"10.1021\/jm901189z","article-title":"Synthesis and biological evaluation of bupropion analogues as potential pharmacotherapies for cocaine addiction","volume":"52","author":"Carroll","year":"2009","journal-title":"J. Med. Chem."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"4731","DOI":"10.1021\/jm1003232","article-title":"Synthesis and characterization of in vitro and in vivo profiles of hydroxybupropion analogues: Aids to smoking cessation","volume":"53","author":"Lukas","year":"2010","journal-title":"J. Med. Chem."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"605","DOI":"10.1016\/j.ejmech.2013.11.019","article-title":"Unraveling the structure\u2013activity relationship of tomatidine, a steroid alkaloid with unique antibiotic properties against persistent forms of Staphylococcus aureus","volume":"80","author":"Chagnon","year":"2014","journal-title":"Eur. J. Med. Chem."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"1914","DOI":"10.1021\/jm401329s","article-title":"Discovery of N-[4-[6-tert-butyl-5-methoxy-8-(6-methoxy-2-oxo-1H-pyridin-3-yl)-3-quinolyl]phenyl]methanesulfonamide (RG7109), a potent inhibitor of the hepatitis C virus NS5B polymerase","volume":"57","author":"Talamas","year":"2014","journal-title":"J. Med. Chem."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"11168","DOI":"10.1021\/acs.joc.6b02152","article-title":"Photocaging of single and dual (similar or different) carboxylic and amino acids by acetyl carbazole and its application as dual drug delivery in cancer therapy","volume":"81","author":"Venkatesh","year":"2016","journal-title":"J. Org. Chem."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"10526","DOI":"10.1021\/jacs.0c03592","article-title":"Two-phase synthesis of taxol","volume":"142","author":"Kanda","year":"2020","journal-title":"J. Am. Chem. Soc."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"150","DOI":"10.1021\/jo00377a027","article-title":"Hypervalent iodine oxidation of silyl enol ethers under Lewis-acid conditions in methanol. A general route to alpha.-methoxy ketones","volume":"52","author":"Moriarty","year":"1987","journal-title":"J. Org. Chem."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"4997","DOI":"10.1002\/chem.200304960","article-title":"The effect of ring nitrogen atoms on the homolytic reactivity of phenolic compounds: Understanding the radical-scavenging ability of 5-pyrimidinols","volume":"9","author":"Valgimigli","year":"2003","journal-title":"Chem.\u2014Eur. J."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"1963","DOI":"10.1021\/ol0705200","article-title":"Synthesis of multisubstituted furans, pyrroles, and thiophenes via ynolates","volume":"9","author":"Shindo","year":"2007","journal-title":"Org. Lett."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"8010","DOI":"10.1021\/acs.joc.3c00033","article-title":"Direct access to strained fused dihalo-aziridino quinoxalinones via C3-alkylation followed by tandem cyclization","volume":"88","author":"Khade","year":"2023","journal-title":"J. Org. Chem."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"1517","DOI":"10.1038\/s41467-021-21825-w","article-title":"Cross-linking peptide and repurposed drugs inhibit both entry pathways of SARS-CoV-2","volume":"12","author":"Zhao","year":"2021","journal-title":"Nat. Commun."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"109349","DOI":"10.1016\/j.cclet.2023.109349","article-title":"Molecules for COVID-19 treatment","volume":"35","author":"Zeng","year":"2024","journal-title":"Chin. Chem. Lett."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"629","DOI":"10.1007\/s11030-020-10176-1","article-title":"COVID-19: Inflammatory responses, structure-based drug design and potential therapeutics","volume":"26","author":"Tripathi","year":"2022","journal-title":"Mol. Divers."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"6806","DOI":"10.1021\/jo060835d","article-title":"Facile synthesis of TMS-protected trifluoromethylated alcohols using trifluoromethyltrimethylsilane (TMSCF3) and various nucleophilic catalysts in DMF","volume":"71","author":"Prakash","year":"2006","journal-title":"J. Org. Chem."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"6754","DOI":"10.1016\/j.tet.2017.10.021","article-title":"MgCl2-catalyzed trifluoromethylation of carbonyl compounds using (trifluoromethyl)trimethylsilane as the trifluoromethylating agent","volume":"73","author":"Cui","year":"2017","journal-title":"Tetrahedron"},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"2547","DOI":"10.1063\/1.454033","article-title":"A multicenter numerical integration scheme for polyatomic molecules","volume":"88","author":"Becke","year":"1988","journal-title":"J. Chem. Phys."},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"580","DOI":"10.1002\/jcc.22885","article-title":"Multiwfn: A multifunctional wavefunction analyzer","volume":"33","author":"Lu","year":"2012","journal-title":"J. Comput. Chem."},{"key":"ref_55","doi-asserted-by":"crossref","first-page":"082503","DOI":"10.1063\/5.0216272","article-title":"A comprehensive electron wavefunction analysis toolbox for chemists, Multiwfn","volume":"161","author":"Lu","year":"2024","journal-title":"J. Chem. Phys."},{"key":"ref_56","doi-asserted-by":"crossref","unstructured":"Parr, R.G. (1980). Density Functional Theory of Atoms and Molecules, Springer.","DOI":"10.1007\/978-94-009-9027-2_2"},{"key":"ref_57","doi-asserted-by":"crossref","first-page":"6647","DOI":"10.1038\/s41467-024-50757-4","article-title":"Catalytic enantioselective intramolecular hydroamination of alkenes using chiral aprotic cyclic urea ligand on manganese (II)","volume":"15","author":"Cui","year":"2024","journal-title":"Nat. Commun."},{"key":"ref_58","doi-asserted-by":"crossref","first-page":"785","DOI":"10.1103\/PhysRevB.37.785","article-title":"Development of the colle-salvetti correlation-energy formula into a functional of the electron density","volume":"37","author":"Lee","year":"1988","journal-title":"Phys. Rev. B"},{"key":"ref_59","doi-asserted-by":"crossref","first-page":"5648","DOI":"10.1063\/1.464913","article-title":"Density-functional thermochemistry. III. The role of exact exchange","volume":"98","author":"Becke","year":"1993","journal-title":"J. Chem. Phys."},{"key":"ref_60","doi-asserted-by":"crossref","first-page":"3098","DOI":"10.1103\/PhysRevA.38.3098","article-title":"Density-functional exchange-energy approximation with correct asymptotic behavior","volume":"38","author":"Becke","year":"1988","journal-title":"Phys. Rev. A"},{"key":"ref_61","doi-asserted-by":"crossref","first-page":"154104","DOI":"10.1063\/1.3382344","article-title":"A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu","volume":"132","author":"Grimme","year":"2010","journal-title":"J. Chem. Phys."},{"key":"ref_62","doi-asserted-by":"crossref","first-page":"1456","DOI":"10.1002\/jcc.21759","article-title":"Effect of the damping function in dispersion corrected density functional theory","volume":"32","author":"Grimme","year":"2011","journal-title":"J. Comput. Chem."},{"key":"ref_63","doi-asserted-by":"crossref","first-page":"213","DOI":"10.1007\/BF00533485","article-title":"The influence of polarization functions on molecular orbital hydrogenation energies","volume":"28","author":"Hariharan","year":"1973","journal-title":"Theoret. Chim. Acta."},{"key":"ref_64","doi-asserted-by":"crossref","first-page":"724","DOI":"10.1063\/1.1674902","article-title":"Self-consistent molecular-orbital methods. IX. An extended gaussian-type basis for molecular-orbital studies of organic molecules","volume":"54","author":"Ditchfield","year":"1971","journal-title":"J. Chem. Phys."},{"key":"ref_65","doi-asserted-by":"crossref","first-page":"6378","DOI":"10.1021\/jp810292n","article-title":"Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions","volume":"113","author":"Marenich","year":"2009","journal-title":"J. Phys. Chem. B"},{"key":"ref_66","doi-asserted-by":"crossref","first-page":"6615","DOI":"10.1039\/b810189b","article-title":"Long-range corrected hybrid density functionals with damped atom\u2013atom dispersion corrections","volume":"10","author":"Chai","year":"2008","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_67","doi-asserted-by":"crossref","first-page":"3297","DOI":"10.1039\/b508541a","article-title":"Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy","volume":"7","author":"Weigend","year":"2005","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_68","doi-asserted-by":"crossref","first-page":"1057","DOI":"10.1039\/b515623h","article-title":"Accurate coulomb-fitting basis sets for H to Rn","volume":"8","author":"Weigend","year":"2006","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_69","doi-asserted-by":"crossref","first-page":"11683","DOI":"10.1021\/jp073974n","article-title":"An evaluation of harmonic vibrational frequency scale factors","volume":"111","author":"Merrick","year":"2007","journal-title":"J. Phys. Chem. A"},{"key":"ref_70","doi-asserted-by":"crossref","first-page":"113249","DOI":"10.1016\/j.comptc.2021.113249","article-title":"Shermo: A general code for calculating molecular thermochemistry properties","volume":"1200","author":"Lu","year":"2021","journal-title":"Comput. Theor. Chem."},{"key":"ref_71","doi-asserted-by":"crossref","first-page":"33","DOI":"10.1016\/0263-7855(96)00018-5","article-title":"VMD: Visual molecular dynamics","volume":"14","author":"Humphrey","year":"1996","journal-title":"J. Mol. Graph."},{"key":"ref_72","doi-asserted-by":"crossref","first-page":"6955","DOI":"10.1021\/jm801007z","article-title":"Linking bisphosphonates to the free amino groups in fluoroquinolones: Preparation of osteotropic prodrugs for the prevention of osteomyelitis","volume":"51","author":"Houghton","year":"2008","journal-title":"J. Med. Chem."},{"key":"ref_73","doi-asserted-by":"crossref","first-page":"7730","DOI":"10.1002\/ejoc.201901655","article-title":"Fast-synthesis of \u03b1-phosphonyloxy ketones as drug scaffolds in a capillary microreactor","volume":"2019","author":"Ramanjaneyulu","year":"2019","journal-title":"Eur. J. Org. Chem."},{"key":"ref_74","doi-asserted-by":"crossref","first-page":"12700","DOI":"10.1039\/c1cc15819h","article-title":"A sustainable byproduct catalyzed domino strategy: Facile synthesis of \u03b1-formyloxy and acetoxy ketones via iodination\/nucleophilic substitution\/hydrolyzation\/oxidation sequences","volume":"47","author":"Zhu","year":"2011","journal-title":"Chem. Commun."},{"key":"ref_75","doi-asserted-by":"crossref","unstructured":"Lee, J.C., Jin, Y.S., and Choi, J.-H. (2001). Synthesis of \u03b1-acetoxy and formyloxy ketones by thallium (III) promoted \u03b1-oxidation. Chem. Commun., 956\u2013957.","DOI":"10.1039\/b102192n"},{"key":"ref_76","doi-asserted-by":"crossref","first-page":"10417","DOI":"10.1002\/chem.202000927","article-title":"Hypervalent iodine(III)-catalysed enantioselective \u03b1-acetoxylation of ketones","volume":"26","author":"Hokamp","year":"2020","journal-title":"Chem.\u2014Eur. J."},{"key":"ref_77","doi-asserted-by":"crossref","first-page":"151707","DOI":"10.1016\/j.tetlet.2020.151707","article-title":"Sulfur-mediated difunctionalization of internal and terminal alkynes for the synthesis of \u03b1-acetoxy ketones","volume":"61","author":"Zhang","year":"2020","journal-title":"Tetrahedron Lett."},{"key":"ref_78","doi-asserted-by":"crossref","first-page":"761","DOI":"10.1007\/s11426-016-0478-3","article-title":"PhI(OAc)2-promoted umpolung acetoxylation of enamides for the synthesis of \u03b1-acetoxy ketones","volume":"60","author":"Chen","year":"2017","journal-title":"Sci. China. Chem."},{"key":"ref_79","doi-asserted-by":"crossref","first-page":"10998","DOI":"10.1039\/C6OB02173E","article-title":"NBS\/DBU mediated one-pot synthesis of \u03b1-acyloxyketones from benzylic secondary alcohols and carboxylic acids","volume":"14","author":"Zhu","year":"2016","journal-title":"Org. Biomol. Chem."},{"key":"ref_80","doi-asserted-by":"crossref","first-page":"339","DOI":"10.1107\/S0021889808042726","article-title":"OLEX2: A complete structure solution, refinement and analysis program","volume":"42","author":"Dolomanov","year":"2009","journal-title":"J. Appl. Crystallogr."},{"key":"ref_81","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1107\/S2053229614024218","article-title":"Crystal structure refinement with SHELXL","volume":"71","author":"Sheldrick","year":"2015","journal-title":"Acta Crystallogr. Sect. 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