New synthetic pathways from gibberellins to antheridiogens isolated from the fern genus anemia

Mark Furber, Lewis N. Mander, Graham L. Patrick

Research output: Contribution to journalArticle

Abstract

Gibbereliin A7 (4) was converted into the antheridiogens 2 and 3 isolated from cultured gametophytes of ferns belonging to the genus Anemia by two independent routes. The first of these established the 9,15-cyclogibberellane
skeleton of 3 by means of an intramolecular alkylation on the 9-ene-l-iodo-16-one 8 which was obtained from the triene acid 7; the 10-hydroxyl of 3 was introduced by syn-SN2' substitution of the 30-mesylate derived from
10. In a second, more efficient approach, lactone 17 was treated with an excess of jV-bromosuccinimide to form dibromide 19, which was also readily converted to a cyclogibberellane derivative, 20. This could be converted
into both antheridiogen 2 from Anemia phyllitidis and antheridiogen 3 from Anemia mexicana. Important features of these syntheses are the solvent-controlled modulation of the effect of the amidine base DBU in the preparation
of 32 and the use of diphenyl- and dimethylboron bromide to effect the contrathermodynamic 1,3-allylic isomerization of lactones 9, 20, and ll,12-dihydro-32.
Original languageEnglish
Pages (from-to)4860-4870
Number of pages11
JournalThe Journal of Organic Chemistry
Volume55
DOIs
Publication statusPublished - 1990
Externally publishedYes

Fingerprint

Gibberellins
Lactones
Amidines
Bromosuccinimide
Mesylates
Alkylation
Isomerization
Bromides
Hydroxyl Radical
Substitution reactions
Modulation
Derivatives
Acids
diphenyl

Cite this

Furber, Mark ; Mander, Lewis N. ; Patrick, Graham L. / New synthetic pathways from gibberellins to antheridiogens isolated from the fern genus anemia. In: The Journal of Organic Chemistry. 1990 ; Vol. 55. pp. 4860-4870.
@article{607e96519b1649c0a55e009e9fdee6df,
title = "New synthetic pathways from gibberellins to antheridiogens isolated from the fern genus anemia",
abstract = "Gibbereliin A7 (4) was converted into the antheridiogens 2 and 3 isolated from cultured gametophytes of ferns belonging to the genus Anemia by two independent routes. The first of these established the 9,15-cyclogibberellaneskeleton of 3 by means of an intramolecular alkylation on the 9-ene-l-iodo-16-one 8 which was obtained from the triene acid 7; the 10-hydroxyl of 3 was introduced by syn-SN2' substitution of the 30-mesylate derived from10. In a second, more efficient approach, lactone 17 was treated with an excess of jV-bromosuccinimide to form dibromide 19, which was also readily converted to a cyclogibberellane derivative, 20. This could be convertedinto both antheridiogen 2 from Anemia phyllitidis and antheridiogen 3 from Anemia mexicana. Important features of these syntheses are the solvent-controlled modulation of the effect of the amidine base DBU in the preparationof 32 and the use of diphenyl- and dimethylboron bromide to effect the contrathermodynamic 1,3-allylic isomerization of lactones 9, 20, and ll,12-dihydro-32.",
author = "Mark Furber and Mander, {Lewis N.} and Patrick, {Graham L.}",
year = "1990",
doi = "10.1021/jo00303a020",
language = "English",
volume = "55",
pages = "4860--4870",
journal = "The Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "ACS Publications",

}

New synthetic pathways from gibberellins to antheridiogens isolated from the fern genus anemia. / Furber, Mark; Mander, Lewis N.; Patrick, Graham L.

In: The Journal of Organic Chemistry, Vol. 55, 1990, p. 4860-4870.

Research output: Contribution to journalArticle

TY - JOUR

T1 - New synthetic pathways from gibberellins to antheridiogens isolated from the fern genus anemia

AU - Furber, Mark

AU - Mander, Lewis N.

AU - Patrick, Graham L.

PY - 1990

Y1 - 1990

N2 - Gibbereliin A7 (4) was converted into the antheridiogens 2 and 3 isolated from cultured gametophytes of ferns belonging to the genus Anemia by two independent routes. The first of these established the 9,15-cyclogibberellaneskeleton of 3 by means of an intramolecular alkylation on the 9-ene-l-iodo-16-one 8 which was obtained from the triene acid 7; the 10-hydroxyl of 3 was introduced by syn-SN2' substitution of the 30-mesylate derived from10. In a second, more efficient approach, lactone 17 was treated with an excess of jV-bromosuccinimide to form dibromide 19, which was also readily converted to a cyclogibberellane derivative, 20. This could be convertedinto both antheridiogen 2 from Anemia phyllitidis and antheridiogen 3 from Anemia mexicana. Important features of these syntheses are the solvent-controlled modulation of the effect of the amidine base DBU in the preparationof 32 and the use of diphenyl- and dimethylboron bromide to effect the contrathermodynamic 1,3-allylic isomerization of lactones 9, 20, and ll,12-dihydro-32.

AB - Gibbereliin A7 (4) was converted into the antheridiogens 2 and 3 isolated from cultured gametophytes of ferns belonging to the genus Anemia by two independent routes. The first of these established the 9,15-cyclogibberellaneskeleton of 3 by means of an intramolecular alkylation on the 9-ene-l-iodo-16-one 8 which was obtained from the triene acid 7; the 10-hydroxyl of 3 was introduced by syn-SN2' substitution of the 30-mesylate derived from10. In a second, more efficient approach, lactone 17 was treated with an excess of jV-bromosuccinimide to form dibromide 19, which was also readily converted to a cyclogibberellane derivative, 20. This could be convertedinto both antheridiogen 2 from Anemia phyllitidis and antheridiogen 3 from Anemia mexicana. Important features of these syntheses are the solvent-controlled modulation of the effect of the amidine base DBU in the preparationof 32 and the use of diphenyl- and dimethylboron bromide to effect the contrathermodynamic 1,3-allylic isomerization of lactones 9, 20, and ll,12-dihydro-32.

U2 - 10.1021/jo00303a020

DO - 10.1021/jo00303a020

M3 - Article

VL - 55

SP - 4860

EP - 4870

JO - The Journal of Organic Chemistry

JF - The Journal of Organic Chemistry

SN - 0022-3263

ER -