197. Ajugarins

Description and references

Diterpenes isolated from the leaves of Ajuga remota (Labiatae). Five different ajugarins have been isolated and identified; of these ajugarins I-III possess antifeedant activity against the African army worm, ajugarin-IV has insecticidal activity, ajugarin V is inactive. Isoln and structure of ajugarins I-III: I. Kubo et al., Chem. Commun. 1976, 949; of ajugarin IV: eidem, ibid. 1982, 618; of ajugarin V: eidem, Chem. Lett. 1983, 223. See also: JP Kokai 82 48979 (1982 to Otsuka). X-ray crystal structure of 12-bromoajugarin-I and absolute configuration: I. Kubo et al., Chem. Commun. 1980, 897; 13C-NMR shift data: J. M. Luteijn et al., Org. Magn. Reson. 19, 95 (1982). Synthetic approaches: D. J. Goldsmith et al., J. Org. Chem. 43, 3182 (1978); J. M. Luteijn, Ae. de Groot, Tetrahedron Lett. 1981, 789. Total synthesis of ajugarin-I: S. V. Ley et al., Chem. Commun. 1983, 503.

Chemical structure

Derivative

Ajugarin-I.

Nomenclature

CAS number: 62640-05-5
[1R-(1α,4aβ,5β,6α,8α,8aα)]-4-[2-[8-(Acetyloxy)-8a-[(acetyloxy)methyl]octahydro-5,6-dimethylspiro[naphthalene-1(2H),2′-oxiran]-5-yl]ethyl]-2(5H)furanone.
C24H34O7; mol wt 434.52.
C 66.34%, H 7.89%, O 25.77%.

Properties

mp 155-157°. uv max (methanol): 212 nm (ε 10000).

Derivative

Ajugarin-II.

Nomenclature

CAS number: 62640-06-6
C22H32O6; mol wt 392.49.
C 67.32%, H 8.22%, O 24.46%.

Properties

8-Hydroxy analog of ajugarin I. mp 188-189°.

Derivative

Ajugarin-III.

Nomenclature

CAS number: 62640-07-7
C24H36O8; mol wt 452.54.
C 63.70%, H 8.02%, O 28.28%.

Properties

1,1-Dihydroxy analog of ajugarin I. mp 243-245°.

Derivative

Ajugarin-IV.

Nomenclature

CAS number: 82225-47-6
C23H34O6; mol wt 406.51.
C 67.96%, H 8.43%, O 23.61%.

Properties

mp 119-120.5°. [α]D 57.5° (c = 0.06 in CHCl3). uv max (ethanol): 215 nm (ε 17000).

Derivative

Ajugarin-V.

Nomenclature

CAS number: 82231-14-9
C22H32O5; mol wt 376.49.
C 70.18%, H 8.57%, O 21.25%.

Properties

mp 217-218°. [α]D 13.5° (c = 0.18 in CHCl3). uv max (ethanol): 210 nm (ε 11000).