Faculty Bibliography

Loline (1) is a small alkaloid that, in spite of its simple-looking structure, has posed surprising challenges to synthetic chemists. It has been known for more than a century and has been the subject of extensive biological investigations, but only two total syntheses have been achieved to date. Here, we report an asymmetric total synthesis of loline that, with less then ten steps, is remarkably short. Our synthesis incorporates a Sharpless epoxidation, a Grubbs olefin metathesis and an unprecedented transannular aminobromination, which converts an eight-membered cyclic carbamate into a bromopyrrolizidine. The synthesis is marked by a high degree of chemo- and stereoselectivity and gives access to several members of the loline alkaloid family. It delivers sufficient material to support a programme aimed at studying the complex interactions between plants, fungi, insects and bacteria brokered by loline alkaloids.

A potentially biomimetic approach toward the complex polyketide A-74528 is described. It is based on highly substituted biaryl compounds, synthesized using advanced cross-coupling and condensation methodologies.

Crocipodin, an unusual benzotropolone pigment, has been isolated from the fruit bodies of the mushroom Leccinum crocipodium. Its structure was determined by spectroscopic methods, particularly 2D NMR spectroscopy. The structure was confirmed by total synthesis, starting from 4-bromocatechol and gallic acid. (C) 2010 Elsevier Ltd. All rights reserved.

A synthetic strategy toward maoecrystal V has been identified. It has been shaped by the necessity to maneuver in sterically hindered molecular environments.

The results of a theoretical investigation on the complex cascade reaction leading to the natural product rubicordifolin are reported. These computations analyze the discrete transformations that are required during the conversion of the vinyl naphthoquinone starting material into the natural product, including two pseudopericyclic cyclizations as well as a diastereoselective, hetero-Diels-Alder reaction.