Superelectrophilic Activation of Phosphacoumarins towards Weak Nucleophiles via Brønsted Acid Assisted Brønsted Acid Catalysis
Zalaltdinova A.V. Sadykova Y.M. Gazizov A.S. Smailov A.K. Syakaev V.V. Gerasimova D.P. Chugunova E.A. Akylbekov N.I. Zhapparbergenov R.U. Appazov N.O. Burilov A.R. Pudovik M.A. Alabugin I.V. Sinyashin O.G.
June 2024Multidisciplinary Digital Publishing Institute (MDPI)
International Journal of Molecular Sciences
2024#25Issue 12
The electrophilic activation of various substrates via double or even triple protonation in superacidic media enables reactions with extremely weak nucleophiles. Despite the significant progress in this area, the utility of organophosphorus compounds as superelectrophiles still remains limited. Additionally, the most common superacids require a special care due to their high toxicity, exceptional corrosiveness and moisture sensitivity. Herein, we report the first successful application of the “Brønsted acid assisted Brønsted acid” concept for the superelectrophilic activation of 2-hydroxybenzo[e][1,2]oxaphosphinine 2-oxides (phosphacoumarins). The pivotal role is attributed to the tendency of the phosphoryl moiety to form hydrogen-bonded complexes, which enables the formation of dicationic species and increases the electrophilicity of the phosphacoumarin. This unmasks the reactivity of phosphacoumarins towards non-activated aromatics, while requiring only relatively non-benign trifluoroacetic acid as the reaction medium.
acid catalysis , arenes , electrophilicity , phosphacoumarins
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FRC Kazan Scientific Center, Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Science, Arbuzova Str., 8, Kazan, 420088, Russian Federation
Kazan National Research Technological University, Karl Marx Str., 68, Kazan, 420015, Russian Federation
Laboratory of Engineering Profile “Physical and Chemical Methods of Analysis”, Korkyt Ata Kyzylorda University, Aitekebie Str., 29A, Kyzylorda, 120014, Kazakhstan
“CNEC” LLP, Dariger Ali Str., Kyzylorda, 120001, Kazakhstan
“DPS Kyzylorda” LLP, Amangeldy Imanov Str., 112A, Kyzylorda, 120008, Kazakhstan
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, 32306, FL, United States
FRC Kazan Scientific Center
Kazan National Research Technological University
Laboratory of Engineering Profile “Physical and Chemical Methods of Analysis”
“CNEC” LLP
“DPS Kyzylorda” LLP
Department of Chemistry and Biochemistry
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