Activation of O-Electrophiles via Structural and Solvent Effects: SN2@O Reaction of Cyclic Diacyl Peroxides with Enol Acetates

Activation of O-Electrophiles via Structural and Solvent Effects: SN2@O Reaction of Cyclic Diacyl Peroxides with Enol Acetates Full article

Journal

Journal of Organic Chemistry
ISSN: 1520-6904 , E-ISSN: 0022-3263

Output data

Year: 2022, Volume: 87, Number: 21, Pages: 13980-13989 Pages count : 10 DOI: 10.1021/acs.joc.2c01634

Authors

Vil' Vera A ¹ , Gorlov Evgenii S ¹ , Shuingalieva Diana V ^2,1 , Kunitsyn Artem Yu ¹ , Krivoshchapov Nikolai V ¹ , Medvedev Michael G ¹ , Alabugin Igor V ³ , Terent'ev Alexander O ¹

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prospect, Moscow 119991, Russian Federation
2	D. Mendeleev University of Chemical Technology of Russia, 9 Miusskaya Square, Moscow 125047, Russian Federation
3	Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States

The reactions of O-electrophiles, such as organic peroxides, with carbon nucleophiles are an umpolung alternative to the common approaches to C–O bond formation. Nucleophilic substitution at the oxygen atom of cyclic diacyl peroxides by enol acetates with the following deacylation leads to α-acyloxyketones with an appended carboxylic acid in 28–87% yields. The effect of fluorinated alcohols on the oxidative functionalization of enol acetates by cyclic diacyl peroxides was studied experimentally and computationally. Computational analysis reveals that the key step proceeds as a direct substitution nucleophilic bimolecular (SN2) reaction at oxygen (SN2@O). CF3CH2OH has a dual role in assisting in both steps of the reaction cascade: it lowers the energy of the SN2@O activation step by hydrogen bonding to a remote carbonyl and promotes the deacylation of the cationic intermediate.

Vil' V.A. , Gorlov E.S. , Shuingalieva D.V. , Kunitsyn A.Y. , Krivoshchapov N.V. , Medvedev M.G. , Alabugin I.V. , Terent'ev A.O.
Activation of O-Electrophiles via Structural and Solvent Effects: SN2@O Reaction of Cyclic Diacyl Peroxides with Enol Acetates
Journal of Organic Chemistry. 2022. V.87. N21. P.13980-13989. DOI: 10.1021/acs.joc.2c01634 WOS Scopus OpenAlex

Web of science:	WOS:000870336900001
Scopus:	2-s2.0-85139843043
OpenAlex:	W4304758149

DB	Citing
OpenAlex	7
Scopus	4
Web of science	6