Affiliation:
1. Givaudan Schweiz AG Fragrances S&T Ingredients Research Kemptpark 50 8310 Kemptthal Switzerland
2. ETH Zürich Dep. of Chemistry and Applied Biosciences Vladimir-Prelog-Weg 1-5/10 8093 Zürich Switzerland
Abstract
AbstractGuaiane sesquiterpenes are an important class of biologically active natural products. Several oxygenated bicyclic but also tricyclic derivatives show unprecedented olfactory activity with great importance in perfumery. Their in vivo syntheses are largely controlled by the intrinsic selectivities of terpene synthases and only a few rearrangements of their hydroazulene skeletons were reported, mostly resulting into terpenoids with decalin motives. Using α‐guaiene and bulnesene, complex rearrangements into novel tri and tetracyclic terpenoids are described herein. The cationic rearrangement mechanisms of their formation based on subsequent 1,2‐H and alkyl shifts promoted by substoichiometric amounts of ethylaluminum dichloride.
Subject
Inorganic Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Drug Discovery,Biochemistry,Catalysis