Synthesis 2024; 56(19): 3074-3082
DOI: 10.1055/a-2352-7116
paper

The Addition of α-Hydroxy-benzylphosphonates to Dialkyl Acetyl­enedicarboxylates; Catalytic Hydrogenation of the Adducts

a   Department of Organic Chemistry and Technology, Faculty of Chemical Technology and Biotechnology, Budapest University of Technology and Economics, 1111 Budapest, Műegyetem rkp. 3, Hungary
b   Egis Pharmaceuticals Plc., Chemical Research Division, 1475 Budapest, PO Box 100, Hungary
,
Cintia Bese
a   Department of Organic Chemistry and Technology, Faculty of Chemical Technology and Biotechnology, Budapest University of Technology and Economics, 1111 Budapest, Műegyetem rkp. 3, Hungary
,
Csenge Kovács
a   Department of Organic Chemistry and Technology, Faculty of Chemical Technology and Biotechnology, Budapest University of Technology and Economics, 1111 Budapest, Műegyetem rkp. 3, Hungary
,
András Dancsó
b   Egis Pharmaceuticals Plc., Chemical Research Division, 1475 Budapest, PO Box 100, Hungary
,
György Keglevich
a   Department of Organic Chemistry and Technology, Faculty of Chemical Technology and Biotechnology, Budapest University of Technology and Economics, 1111 Budapest, Műegyetem rkp. 3, Hungary
› Institutsangaben
This project was supported by the National Research, Development and Innovation Office, Hungary (K134318).


Abstract

α-Hydroxy-benzylphosphonates obtained by the Pudovik reaction of substituted benzaldehydes and dialkyl phosphites were added to the triple bond of dialkyl acetylenedicarboxylates. Optimum conditions involved a 24 hours stirring in the presence of 10% diazabicycloundecene in dichloromethane to afford the adducts as a mixture of predominant E- and a minor Z-isomers in 75–90% yields after flash chromatography. The structures of the geometrical isomers were confirmed by NOE- and ROE-measurements. Catalytic hydrogenation of the olefinic moiety of the adducts led to the diastereoisomers of corresponding saturated derivatives.

Supporting Information



Publikationsverlauf

Eingereicht: 24. Mai 2024

Angenommen nach Revision: 25. Juni 2024

Accepted Manuscript online:
25. Juni 2024

Artikel online veröffentlicht:
18. Juli 2024

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