Substituents in Aromatic Aldehydes Determine Conditions and Chemoselectivity of Their Condensation with Trialkyl Phosphonoacetates

Substituents in Aromatic Aldehydes Determine Conditions and Chemoselectivity of Their Condensation with Trialkyl Phosphonoacetates Full article

Journal

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

Output data

Year: 2026, Volume: 91, Number: 30, Pages: 10473–10489 Pages count : DOI: 10.1021/acs.joc.6c00989

Authors

Kuleshov Andrey V. ¹ , Andreev Ivan A. ² , Ignat’eva Elisaveta M. ^3,1 , Ratmanova Nina K. ² , Ivanova Olga A. ² , Levina Irina I. ⁴ , Trushkov Igor V. ¹

Affiliations

1	N.D. Zelinsky Institute of Organic Chemistry Russian Academy of Sciences, Leninsky Pr. 47, Moscow 119991, Russia
2	M.V. Lomonosov Moscow State University, Department of Chemistry, Leninskie Gory 1-3, Moscow 119991, Russia
3	MIREA − Russian Technological University, Lomonosov Institute of Fine Chemical Technologies, Vernadsky Pr. 78, Moscow 119454, Russia
4	Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Kosygina 4, Moscow 119334, Russia

Although the Knoevenagel condensation of aldehydes with various CH-acids has been known for more than 130 years, the efficiency of this reaction for phosphonoacetates remains poorly understood. We found that the preferred conditions for the formation of target 3-(hetero)aryl-2-(dialkoxyphosphoryl)acrylates depend on the electronic properties of the aldehyde used. Specifically, for the Knoevenagel condensation of trialkyl phosphonoacetates with electron-deficient (hetero)aromatic aldehydes, the best results are achieved using a combination of piperidine and acetic acid as a catalyst, whereas for aldehydes containing an electron-rich aromatic group, higher yields were obtained using the pyrrolidine/acetic acid catalytic system. Preferred amines for catalyzing the reactions of aldehydes with diverse electroneutral aromatic groups were also identified. Secondary amines themselves can also be used to carry out this reaction without loss of efficiency. In contrast, tertiary amines were ineffective both alone and in combination with carboxylic acids. Based on the obtained data, the mechanistic picture of the Knoevenagel condensation of trialkyl phosphonoacetates and its competition with the Horner–Wadsworth–Emmons condensation was refined.

Kuleshov A.V. , Andreev I.A. , Ignat’eva E.M. , Ratmanova N.K. , Ivanova O.A. , Levina I.I. , Trushkov I.V.
Substituents in Aromatic Aldehydes Determine Conditions and Chemoselectivity of Their Condensation with Trialkyl Phosphonoacetates
Journal of Organic Chemistry. 2026. V.91. N30. P.10473–10489. DOI: 10.1021/acs.joc.6c00989 OpenAlex

Submitted:	Apr 25, 2026
Published online:	Jul 31, 2026

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