A substance produced by the male Dried Bean beetle has been characterised as methyl n-tetradeca-trans-2,4,5-trienoate. This is thought to be the first example of an allenic compound occurring in the animal kingdom. It is presumed to be a sex attractant.

(-)Methyl n-tetradeca <-trans-2,4,5-trienoate, an allenic ester produced by the male dried bean beetle, Acanthoscelides obtectus (Say).

Catalytic Intramolecular Wittig Reaction Based on a Phosphine/Phosphine Oxide Catalytic Cycle for the Synthesis of Heterocycles

Palladium-Catalyzed Oxidative Cyclocarbonylation of Isoquinolones with CO via C-H/N-H Bond Cleavage: Easy Access to Isoindolo[2,1-b]isoquinoline-5,7-dione Derivatives

Hybrid compounds based on N-maleopimarimides containing a triazole-ring pharmacophore were prepared via 1,3-dipolar cycloaddition of methyl-2-azidoacetate to allenoates.

Synthesis of 1,2,3-Triazole Derivatives from 2,3-Dienoates of Methyl Maleopimarate

Regiospecific synthesis of conjugates containing a diterpenoid fragment and a pyrazole-ring pharmacophore by 1,3-dipolar cycloaddition of diazomethane to allenoates in the presence of Et3N was demonstrated.

Synthesis of New Pyrazole–Methylmaleopimarate Conjugates

In continuation of research on the synthesis of stable allenoates of N-substituted amino acids [1–3], we proposed a synthetic pathway to 2,3-dienoate 1 as a convenient synthon for further transformations that contained a maleopimaric acid moiety in its structure. Maleopimaric acid and its derivatives are known to exhibit high biological activity [4, 5]. Allene 1 was synthesized from methyl maleopimarate (2) and -aminobutyric acid (3, GABA). The N-substituted GABA of methyl maleopimarate (4) was obtained via direct fusion or condensation in DMF in yields of 52 and 72%, respectively. Then, 4 was refluxed in anhydrous C6H6 with an excess of thionylchloride for 3 h. The resulting acid chloride and Et3N gave ketene 5, which reacted with methyl(triphenylphosphoranylidene)acetate afforded the corresponding allenoate 1 in 66% yield (Scheme 1).

Synthesis of a 2,3-Dienoate Based on Methyl Maleopimarate

Isoindoloisoquinoline contains two pharmacophore fragments and therefore serves as major structural fragment of a number of biologically active compounds used in clinical practice [1]. Isoquinoline alkaloids are widespread in nature [2, 3]. Recently, nuevamine [4], jamtine [5], and hirsutine [6] alkaloids inclusing isoindolo[1,2-a]isoquinoline fragment have been isolated from Cocculus hirsutus (L.) and Berberis darwinii Hook plants. Isoindolo[1,2-a]isoquinoline derivatives can be obtained from isoquinoline [7] and isoindole [8] derivatives. However, these methods utilize the poorly accessible starting materials.

A. M. Gumerov

Papers

Synthesis of New Pyrazole–Methylmaleopimarate Conjugates

Synthesis of a 2,3-Dienoate Based on Methyl Maleopimarate

Synthesis of isoindolo[2,1-b]isoquinoline-5,7-dione via the wittig intramolecular cyclization

New Synthetic Method for the Racemic form of the Bean Weevil Acanthoscelides obtectus Male Pheromone