Explorations on the asymmetric total synthesis of isoschizogamine.

Two approaches to the synthesis of isoschizogamine were reported. Both routes utilized an efficient aza-Claisen rearrangement to establish the absolute stereochemistry of the all-carbon quaternary center in the natural product. In the first approach, a highly diastereoselective (10:1) hetero-Diels-Alder reaction was utilized to reach a densely functionalized tetrahydroquinoline derivative as an advanced intermediate to the targeted alkaloid.

Phosphine-mediated coupling of gramines with aldehydes: a remarkably simple synthesis of 3-vinylindoles.

A new and practical synthesis of terminally substituted 3-vinylindoles is described involving tributylphosphine-mediated coupling of gramines with aldehydes.

Chemoselective cyclizations of divinyl ketones to cyclohexenones mediated by Lewis acid and base.

[reaction: see text] Chemoselective cyclizations of divinyl ketones to cyclohexenones mediated by a sterically demanding Lewis acid and an amine base have been accomplished under mild reaction conditions. The extension of this methodology to the synthesis of eight-membered rings is also demonstrated.

Remarkably facile hexatriene electrocyclizations as a route to functionalized cyclohexenones via ring expansion of cyclobutenones.

This Communication describes a cascade reaction sequence that leads to highly functionalized cyclohexenones starting from reaction of cyclobutenones with alpha-lithio-alpha,beta-unsaturated sulfones and amides. The hexatriene-cyclohexadiene cyclization steps presumed to be involved in these transformations are among the most facile hexatriene electrocyclizations reported thus far.

Efficient construction of cyclopenta[b]quinoline core of isoschizozygane alkaloids via intramolecular formal hetero-Diels-Alder reaction.

[reaction: see text] Acid-catalyzed condensation of aromatic amines with delta,epsilon-unsaturated aldehydes, followed by intramolecular formal hetero Diels-Alder reaction, is described as a potential route to the cyclopenta[b]quinoline substructure of isoschizozygane alkaloids. Reactions are highly diastereoselective and produce adducts with up to four contiguous stereocenters.