2 NATURAL PRODUCT SYNTHESIS BY UTILIZING RING-OPENING REACTION OF β-PROPIOLACTONE

Sato T., Kawara T., Kawashima M., Noda A., Naruse K., Fujisawa T.

doi:10.24496/tennenyuki.23.0_9

The regioselective ring cleavage of β-propiolactone was established by the use of diorganocuprates or Grignard reagents in the presence of a copper(I) catalyst to afford β-substituted propionic acids in high yields. The reaction provides a useful method for three carbon homologation terminating with a carboxyl function, and can be used for the synthesis of several natural products. For the synthesis of a macrolide, a copper catalyzed reaction of β-propiolactone with 12-methoxydodecanylmagnesium bromide (2), which was derived from available 1,12-dodecanediol, was used to construct 15-methoxypentadecanoic acid (3), which was easily converted into exaltolide (5). One-pot synthesis of cis-4-alkenoic acids, which are known as a component of perfumes and flavors, was achieved by the reaction of β-propiolactone with cis-1-alkenylcuprates prepared form Grignard reagents, copper(I) iodide and acetylene. Among them, cis-4-heptenoic acid was easily transformed into cis-jasmone (11) via cis-8-undecen-2,5-dione (10). β-Methyl-β-propiolactone was used as an important component for the terpene synthesis. Homoprenyl Grignard reagent reacted with the lactone in the presence of a copper(I) catalyst to afford citronellic acid (12), which was converted into various monoterpenes, such as citronellol, geraniol (14) and nerol (15). Further, by utilizing the SN2 type of ring-opening reaction of (R)-β-methyl-β-propiolactone, which was easily obtained from (S)-(+)-3-bromobutyric acid resolved by an optically active amine, (S)-ar-turmerone (18) was synthesized in high enantiomeric excess.

2 NATURAL PRODUCT SYNTHESIS BY UTILIZING RING-OPENING REACTION OF β-PROPIOLACTONE

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