Reactions of Diferrocenylmorpholino- and -Methylsulfanyl-cyclopropenylium Salts with β-Dicarbonyl Compounds and Diethyl Malonate

• Published in: Synthetic communications 2010-02, Vol.40 (6), p.839-854
• Main Authors: Klimova, Elena I., Stivalet, J. M. Méndez, Klimova, T., Flores-Alamo, M., Backinowsky, L. V., Ortiz-Frade, Luis, Garcia, M. Martinez
• Format: Article
• Language: English
• Subjects: 3-[Acyl(ethoxycarbonyl)]methyl-3-methylsulfanyl-1,2-diferrocenylcyclopropenes; 3-[acyl(ethoxycarbonyl)]methyl-3-morpholino-1,2-diferrocenylcyclopropenes; diferrocenyl(methylsulfanyl)cyclopropenylium; diferrocenyl(morpholino)cyclopropenylium; electrochemistry; ethoxycarbonyl group migration; ethyl 2-acyl-3,4-diferrocenyl-5-methylsulfanylpenta-2,4-dienoates
• ISSN: 0039-7911; 1532-2432
• DOI: 10.1080/00397910903014240

2,3-Diferrocenyl-1-morpholinocyclopropenylium tetrafluoroborate reacts with ethyl acetoacetate, ethyl benzoylacetate, and diethyl malonate in the presence of triethylamine to yield 3-[acyl(ethoxycarbonyl)]-, 3-(diethoxycarbonyl)-methyl-3-morpholino-1,2-diferrocenylcyclopropenes (3a-c), and 3-[acyl(ethoxycarbonyl)]- and (diethoxycarbonyl)-methylidene-1,2-diferrocenylcyclopropenes (4a-c) in a ca. 1:1.5 ratio. 2,3-Diferrocenyl-1-methylsulfanylcyclopropenylium iodide with the same substrates affords compounds 4a,b (∼10-15%), 3-[acyl(ethoxycarbonyl)]methyl-3-methylsulfanyl-1,2-diferrocenylcyclopropenes (5a,b) (∼8-10%), 2-acyl-3,4-diferrocenyl-5-methylsulfanylcyclopentadienones (6a,b), ethyl 2-acyl-3,4-diferrocenyl-5-methylsulfanylpenta-2,4-dienoates (7a,b; 8a,b), and ethyl 3,4-diferrocenyl-2-methylsulfanyl-6-oxohexa(hepta)-2,4-dienoates (9a,b). The spatial structure of ethyl Z,E-3,4-diferrocenyl-2-methylsulfanyl-6-oxohepta-2,4-dienoate (9b) was established based on the data from x-ray diffraction analysis. Electrochemical properties of 3-[acyl(ethoxycarbonyl)]- and (diethoxycarbonyl)-methylidene-1,2-diferrocenylcyclopropenes (4a-c) are studied.