It all began with an error: the nomofungin/communesin story.

The communesin/nomofungin/perophoramidine story is an impressive example of how biogenetic considerations can lead to the correction of structural misassignments and inspire synthetic chemists with new, fruitful ideas. Intensive studies by a number of research groups culminated in the total synthesis of perophoramidine by the Funk research group in 2004. In 2007, Qin and co-workers completed the first total synthesis of a communesin.

Total synthesis of epi-7-deoxypancratistatin via aza-Payne rearrangement and intramolecular cyclization.

[reaction: see text] epi-7-Deoxypancratistatin containing the cis-fused phenanthridone core was synthesized in 12 steps from bromobenzene. Key features of this synthesis include the enzymatic oxidation of bromobenzene with toluene dioxygenase, selective opening of a cyclic sulfate over an aziridine with oxygen nucleophiles, and an intramolecular Lewis acid-catalyzed cyclization onto an epoxy conduramine derived via aza-Payne rearrangement.

Recent progress in the total synthesis of naphthyridinomycin and lemonomycin tetrahydroisoquinoline antitumor antibiotics (TAAs).

In this tutorial review, which should be of general interest to synthetic organic chemists at large, recent progress in the total synthesis of the tetrahydroisoquinoline antitumor antibiotics cyanocycline A, naphthyridinomycin, bioxalomycin alpha2, and lemonomycin is highlighted in detail and some biological background information is given as well. Preparations of truncated derivatives and uncompleted synthetic approaches are also described. The literature coverage includes the newest research results through the year 2008.

3,6-Dihydroxy-2-(11-phenylundecanoyl)cyclohex-2-en-1-one from Virola venosa bark.

The structure of the title compound, C23H32O4, an arylalkanone isolated from the petroleum ether fraction of the ethanol extract of the bark of Virola venosa, has been established by NMR spectroscopy and, for the first time, by X-ray structure analysis. Two independent molecules of the same enantiomer are present in the unit cell. Both molecules exhibit an intramolecular hydrogen bond, which can be correlated with a rare signal observed at 18.28 p.p.m. in the 1H NMR spectrum. The packing, in space group P1, is determined by a pseudo-center of symmetry leading to a short intermolecular contact, which is present in one molecule but does not occur in the other. As a consequence, the O-C-C-O torsion angles [-16.9 (3) and -12.7 (3) degrees ] through the ketone and its adjacent hydroxy group are significantly different in the two molecules.

Total synthesis and biological evaluation of Amaryllidaceae alkaloids: narciclasine, ent-7-deoxypancratistatin, regioisomer of 7-deoxypancratistatin, 10b-epi-deoxypancratistatin, and truncated derivatives.

Biocatalytic approaches have yielded efficient total syntheses of the major Amaryllidaceae alkaloids, all based on the key enzymatic dioxygenation of suitable aromatic precursors. This paper discusses the logic of general synthetic design for lycoricidine, narciclasine, pancratistatin, and 7-deoxypancratistatin. Experimental details are provided for the recently accomplished syntheses of narciclasine, ent-7-deoxypancratistatin, and 10b-epi-deoxypancratistatin via a new and selective opening of a cyclic sulfate over aziridines followed by aza-Payne rearrangement. The structural core of 7-deoxypancratistatin has also been degraded to a series of intermediates in which the amino inositol unit is cleaved and deoxygenated in a homologous fashion. These truncated derivatives and the compounds from the synthesis of the unnatural derivatives have been tested against six important human cancer cell lines in an effort to further develop the understanding of the mode of action for the most active congener in this group, pancratistatin. The results of the biological activity testing as well as experimental, spectral, and analytical data are provided in this manuscript for all relevant compounds.