4316-49-8

Upstream product

• 119681-13-9 (2R,5RS,7S)-Exogonal 
• 91006-92-7 (2R,5RS,7S)-2-(2'-Hydroxyethyl)-7-methyl-1,6-dioxaspiro<4.4>nonane 
• 137846-91-4 tert-Butyl-dimethyl-[2-((2S,5S,7R)-7-methyl-1,6-dioxa-spiro[4.4]non-2-yl)-ethoxy]-silane 
• 119681-11-7 2-(4'-hydroxy-1'-oxo-6'-tetrahydropyranyloxy)-4-pentanolide 
• 119681-12-8 2-Methyl-7-[2-(tetrahydro-pyran-2-yloxy)-ethyl]-1,6-dioxa-spiro[4.4]nonane 
• 3620-18-6 3-acetyl-5-methyldihydrofuran-2(3H)-one 
• 91006-92-7 racemic Exogonol 
• 60551-20-4 γ-(carboxymethyl)-γ-butyrolactone 
• 119681-13-9 exogonal 

Downstream Products

• 20969-25-9 racemic Methyl exogonate 
• 627-93-0 hexanedioic acid dimethyl ester 

Relevant academic research and scientific papers

Synthesis of Exogonic Acid and Related Compounds

Hydroxymercuration, cyclization, and reduction of appropriate hydroxy ketones or enones carrying a suitably located α,β-unsaturated ester function is an efficient route to exogonic acid (2-(carboxymethyl)-7-methyl-1,6-dioxaspirononane), a resin constituent of the Brazilian tree Ipomoea operculata (Martin), and related and spiroketal systems.Procedures incorporating stereocontrol at C-2 and C-7 of exogonic acid are also reported and involve sequential alkylation with epoxypropane and 1,2-epoxy-4-(tetrahydropyranyloxy)butane of anions (or dianions) derived from methyl acetoacetate or acetone dimethylhydrazone.

Absolute Stereochemistry of Exogonic Acid

Exogonic acid (2-(carboxymethyl)-7-methyl-1,6-dioxaspirononane), a resin constituent of the Brazilian tree Ipomoea operculata (Martin) is demonstrated to be predominantly the E,E and Z,Z diastereomers, with the 2S,5S,7R and 2S,5R,7R configurations, respectively.Minor amounts of the 2R,5S,7R E,Z and 2R,5R,7R Z,E isomers are also present.These conclusions are based on chiral gas chromatographic analyses of suitable derivatives and enantioselective syntheses employing (S)-1,2-epoxypropane and (2S)-4-oxy>-1,2-epoxybutane as alkylating agents for anions of acetone N,N-dimethylhydrazone.

Naturally Occurring Spirocyclic Ketals from Lactones. 3

Our earlier methodology for the synthesis of 1,6-dioxaspirononane and 1,6-dioxaspirodecane derivatives has been applied to the synthesis of substances found in the mandibular gland secretions of Andrena bees.Use of optically active propylene oxide as a precursor gave 7-methyl-1,6-dioxaspirodecane, reported from Andrena and Vespula species, in 80percent optical purity as shown by 13C NMR spectroscopy with a chiral shift reagent.Adaptations of the method allowed synthesis of a tetramethyl-1,6-dioxaspirononene found in Japanese hop oil and of exogonic acid, a resin constituent of the Brazilian tree Ipomoae operculata (Martin).We have also simplified our synthesis of chalcogran, 2-ethyl-1,6-dioxaspirononane, by using γ-caprolactone and the lithium reagent prepared from 3-bromo-1-propyl 1-ethoxyethyl ether.