O. N. Yudina

Synthesis of Z,Z-Trishomofarnesal tert-butylimine

A highly stereoselective method was developed for the preparation of Z,Z-trishomofarnesal tert-butylimine, a key block synthone required for the construction of polyprenols with a nonnatural configuration of the “head” end of the chain, using as a basis the controlled condensation of aldehydes with aldimines. It was shown that introduction into the condensation of aldehydes containing an acetal grouping at the ω-position results in the formation of considerable amounts of aldols. The use of α-trimethylsilyl derivatives of aldimines makes it possible to dispense with this process and to direct the reaction toward the desired Eacroleins.

Directed aldol condensation as a stereoselective method for the synthesis of Z-trisubstituted olefins

Conclusions1.The directed aldol condensation with higher aldehydes and aldimines, including functionally substituted compounds, can serve as a highly stereoselective preparative method for the production of the E-disubstituted acroleins, which are readily transformed into the corresponding Z-trisubstituted olefins.2.The potentialities of the method are illustrated by the synthesis of the heptaprenols ωtttcccOH and ωtttcctOH.

Establishment of the configuration of derivatives of 2Z-butene-1,4-diol by1H NMR spectroscopy

Abstract1H NMR spectroscopy and the PANIC program for obtaining calculated spectra were used to show that the Z-configuration of the C=C bond is retained in the conversions of 2Z-butene-1,4-diol to the corresponding monobromide and monochloride and in the reaction of this monobromide with amylmagnesium bromide in the presence of the Kochi reagent (Li2CuCl4) and with the tert-butylimine of acetaldehyde.

Synthesis of modified hexaprenol WC5OH from glutaraldehyde derivatives

A new procedure was developed for building linear Z-isoprenoids from glutaraldehyde derivatives as nonisoprenoid precursors, and is illustrated by the synthesis of hexaprenol WC5OH.

Synthesis of two hexaprenols modified with respect to position of hydroxy group

Conclusions1.A highly stereospecific synthesis of two hexaprenols, modified with respect to the position of the hydroxy group, was carried out by the method of directed aldol condensation.2.A highly stereoselective method has been developed for synthesizing of a common precursor of multipurpose syntones, -4-methylhex-4Z-en-al and 4-benzyloxyhex-4E-en-l-al.