The Awakening of a Sleeping Beauty: The ortho Photocycloaddition in the Total Synthesis of Protoilludane- and Prezizaene-Type ­Sesquiterpenes

Dedicated to Professor Masahiro Murakami.

Abstract

Photochemical cascade (domino) reactions provide a unique opportunity for the construction of complex molecular architectures. Specifically, an intramolecular ortho photocycloaddition of 7-(alkenyloxy)-indanones triggers a sequence of consecutive reactions that can lead in a single operation to the complete skeleton of two important classes of sesquiterpenes: protoilludanes and prezizaenes. In the former case, two transformations follow the initial photocycloaddition, while in the latter case, there are three consecutive transformations, two of which are initiated by a photon. Remarkably, the reaction cascades proceed with exquisite diastereoselectivity, generating three (protoilludane) or five (prezizaene) stereogenic centers with defined relative configurations.

1 Introduction

2 First Encounter and Initial Studies

3 Protoilludane-Type Sesquiterpenes

4 Prezizaene-Type Sesquiterpenes

5 Enantioselectivity

6 Perspective and Summary

Key words

cycloaddition - domino reaction - electrocyclic reactions - photochemistry - stereoselective synthesis - terpenoids

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