Related Experiment Video
Updated: Jul 9, 2025

Preparation of Enantiopure Non-Activated Aziridines and Synthesis of Biemamide B, D, and epiallo-Isomuscarine
Published on: June 13, 2022
Unified Synthesis of 2-Isocyanoallopupukeanane and 9-Isocyanopupukeanane through a "Contra-biosynthetic"
Melissa A Hardy1, Jack Hayward Cooke1, Zhitao Feng2
1Department of Chemistry, University of California, Berkeley, CA 94720, USA.
Abstract:
Herein, we describe our synthetic efforts toward the pupukeanane natural products, in which we have completed the first enantiospecific route to 2-isocyanoallopupukeanane in 10 steps (formal synthesis), enabled by a key Pd-mediated cyclization cascade. This subsequently facilitated an unprecedented bio-inspired "contra-biosynthetic" rearrangement, providing divergent access to 9-isocyanopupukeanane in 15 steps (formal synthesis). Computational studies provide insight into the nature of this rearrangement.
Related Concept Videos
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
Preparation of 1° Amines: Hofmann and Curtius Rearrangement Overview
Preparation of 1° Amines: Hofmann and Curtius Rearrangement Mechanism
[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement
Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation
Aldehydes and Ketones with HCN: Cyanohydrin Formation Overview

