Larry Overman began his career at University of California, Irvine in June 1971. The Irvine graduate program was small and thus in his early work Overman frequently performed experiments himself,[1] including his initial discovery of the Overman rearrangement.[2]
Palladium emerged as the metal of choice for this reaction, and this led to a long-term interest in palladium catalysis, including the palladium(II)-catalyzed Cope rearrangement,[3] and later work on intramolecular cascading Heck reactions.[4]
Overman has performed many total syntheses of natural products, beginning with (±)-pumiliotoxin C (with Peter Jessup) in the late seventies.[5] This interest was spurred on by a 1977 sabbatical visit by Samuel J. Danishefsky.[1]
Overman has also worked extensively on the aza-Cope-Mannich reaction, originally designed[1] to solve a stereoelectronic problem in the total synthesis of gephyrotoxin.[6]
This reaction is described by Overman as "robust",[1] and was subsequently used in the total syntheses of several natural products, for example (–)-strychnine.[7] A ring-enlarging version of the reaction was used in the synthesis of secondary metabolites such as actinophyllic acid.[8] A related reaction, a Prins-Pinacol cascade which produces a tetrahydrofuran, has also been used extensively by the Overman group,[9] for example in the total synthesis of (–)-magellanine, a Lycopodiumalkaloid.
