Chemistry and Biology of Mycotoxins and Related Fungal Metabolites

Macrolactonizations in the Total Synthesis of Natural Products

Products A. Parenty,† X. Moreau,†,§ Gilles Niel,‡ and J.-M. Campagne*,†,‡ †Institut de Chimie des Substances Naturelles, Avenue de la Terrasse, F-91198 Gif sur Yvette, France Institut Lavoisier de Versailles, UMR CNRS 8180, Universite ́ de Versailles-Saint-Quentin-en-Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles Cedex, France ‡Institut Charles Gerhardt, UMR5253, Ecole Nationale Supeŕieure de Chimie, 8 rue de l’Ecole Normale, F-34296 Montpellier, France

Update 1 of: macrolactonizations in the total synthesis of natural products.

Further reactions of t-butyl 3-oxobutanthioate and t-butyl 4-diethyl-phosphono-3-oxobutanthioate : Carbonyl coupling reactions, amination, use in the preparation of 3-acyltetramic acids and application to the total synthesis of fuligorubin A.

https://pubs.rsc.org/en/content/articlepdf/2014/NP/C4NP00015C

Recent advances in the field of bioactive tetronates

Dianions generated from S-t-butyl acetothioacetate (1) were alkylated with a variety of electrophiles at the γ-carbon centre. Treatment of the alkylated products with 2-hydroxy esters in the presence of silver(I) salts gave transesterified acetoacetate derivatives in good yields. These acetoacetates were cyclised efficiently to acyltetronic acid derivatives using tetrabutyl ammonium fluoride in THF solution at room temperature. By an appropriate choice of substituents the total syntheses of the fungal metabolite natural products carlosic, carolic, and carlic acids have been achieved.

Preparation of acyltetronic acids using t-butyl acetothioacetate: total synthesis of the fungal metabolites carolic, carlosic, and carlic acids

Preparation of β-ketomacrolactones and β-ketodiolides using S-t-butyl 3-oxobutanethioate and S-t-butyl 4-diethylphosphono-3-oxobutanethioate

Regiospecific alkylation of β-ketothioesters and use in the synthesis of acyl-tetronic acids

Dianions from t-butyl acetothioacetate may be alkylated at the γ-carbon atom with suitably protected iodoalkanols to afford useful precursors for dimerisation to novel bis-β-ketomacrolides in the presence of copper(I) trifluoroacetate.

The use of t-butyl acetothioacetate as a route to bis-β-ketomacrolides

tert-Butyl acetothioacetate and its use in synthesis: 3-Acetyl-4-hydroxy-5,5-dimethylfuran-2(4H)-one



intermediate: S-tert-butyl 3-oxobutanthioate




intermediate: 1-Carbomethoxy-1-methylethyl 3-oxobutanoate.




product: 3-Acetyl-4-hydroxy-5,5-dimethylfuran-2(5H)-one.





Keywords:

acylation;
acylation;
addition, to CO;
annulation, heterocyclic-[5];
cyclization, condensation;
ring opening reactions;
transesterification;
silver(I) trifluoroacetate;
tetrahydrofuran;
mercaptans, stench

Christina M. J. Fox

Papers

Preparation of acyltetronic acids using t-butyl acetothioacetate: total synthesis of the fungal metabolites carolic, carlosic, and carlic acids

Preparation of β-ketomacrolactones and β-ketodiolides using S-t-butyl 3-oxobutanethioate and S-t-butyl 4-diethylphosphono-3-oxobutanethioate

Regiospecific alkylation of β-ketothioesters and use in the synthesis of acyl-tetronic acids

The use of t-butyl acetothioacetate as a route to bis-β-ketomacrolides

tert‐Butyl Acetothioacetate and Its Use in Synthesis: 3‐Acetyl‐4‐hydroxy‐5,5‐dimethylfuran‐2(4H)‐one