Gummiferolic acid (1) is an atisenoic acid derivative that shows phytohormonal activity. In order to increase this activity the natural product, after careful functionalisation, was subjected to several reaction conditions to provoke the contraction of the ring B from six to five members. Pinacolinic acid and basic rearrangements led to the desired gibberellin-like epimers (atisagibberellaldehydes) 28 and 29.
GrandeM, MoránJR, MacíasMJ, MancheñoB. (1993) Carbon-13 nuclear magnetic resonance spectra of some tetracyclic diterpenoids isolated from Elaeoselinum species. Phytochemical Analysis, 4, 19–24;
2.
GrandeM, MacíasMJ, MancheñoB, SeguraM, ZarzoA. (1991) New kaurane diterpenoids from the aerials parts of Distichoselinum tenuifolium. Journal of Natural Porducts, 54, 866–869;
3.
GrandeM, MancheñoB, SánchezMJ. (1991) Elasclepial and other tetracyclic diterpenoids from Elaeoselinum asclepium. Phytochemistry, 30, 1977–1982;
4.
PinarM, RodríguezB, AlemanyA. (1978) Gummiferolic acid, a new ent-atis-16-ene diterpenoid from Margotia gummifera. Phytochemistry, 17, 1637–1640.
5.
GhisalbertiEL. (1997) The biological activity of naturally occurring kaurane diterpenes. Fitoterapia, 8, 303–326.
6.
ManderLN. (2003) Twenty years of gibberellin research. Natural Product Reports, 20, 49–69;
7.
MacMillanJ. (1997) Biosynthesis of the gibberellin plant hormones. Natural Product Reports, 14, 221–243.
8.
VillalobosN, MartínL, MacíasMJ, MancheñoB, GrandeM. (1994) Gibberellin-like activity of some tetracyclic diterpenoids from Elaeoselinum species and their derivatives. Phytochemistry, 37, 635–639.
9.
HansonJR, SarahFY, FragaBM, HernándezMG. (1979) The microbiological preparation of two ‘atisagibberellins’. Phytochemistry, 18, 1875–1876.
10.
NodeM, HoriH, FujitaE. (1976) Terpenoids. Part XXXVIII. Ring B contraction of kaurenolides and related compounds into gibberellane-type compounds. Journal of the Chemical Society Perkin Transactions I, 2144–2149;
11.
GonzálezAG, FragaBM, HernándezMG, LuisJG. (1978) Synthesis of 4-epi-gibbellerin A12 from ent-7a,18-dihydroxy-kaur-16-ene. Tetrahedron Letters, 37, 3499–3500;
12.
GonzálezAG, FragaBM, LarrugF, LuisJG. (1975) Reagrupamiento tipo ácido bencílico en diterpenos tetracíclicos. Anales de Química, 71, 733–734.
13.
GaltHB. HansonJR. (1965) New metabolites of Gibberella fujikuroi. Part VII. The preparation of some ring-B nor-derivatives, Journal of the Chemical Society, 1565–1570;
14.
FragaBM, GuillermoR, HansonJR. (1990) The partial synthesis of 7β-hydroxyatisenolide and atisagibberellin A12 dimethyl esters. Journal of Chemical Research (S), 99; (M), 728–736.
15.
ShionharaT, SuzukiK. (2003) Facile one-pot procedure for Et3Al-promoted asymmetric pinacol type rearrangement. Synthesis, 141–146;