A Modular Approach for the Synthesis of Natural and Artificial Terpenoids

Abstract

Many terpenoids with isoprene unit(s) demonstrating critical biological activities have been isolated and characterized. In this study, we have developed a robust chem‐stamp strategy for the construction of the key isoprene unit, which consists of two steps: one‐carbon extension of aldehydes to the alkenyl boronates by the boron‐Wittig reaction and the rhodium‐catalyzed reaction of alkenyl boronates with 2,3‐allenols to yield enals. This chem‐stamp could readily be applied repeatedly and separately, enabling the modular concise synthesis of many natural and pharmaceutically active terpenoids, including retinal, β‐carotene, vitamin A, tretinoin, fenretinide, acitretin, ALRT1550, nigerapyrone C, peretinoin, and lycopene. Owing to the diversified availability of the starting materials, aldehydes and 2,3‐allenols, creation of new non‐natural terpenoids has been realized from four dimensions: the number of isoprene units, the side chain, and the two terminal groups.

Triterpenoids from Cyclocarya paliurus: Structure, biosynthesis, biological activities

“…Terpenoids are natural compounds formed by isoprene [19] . The basic nucleus of most triterpenoids is composes 30 carbon atoms, which can be regarded as the polymerization of six isoprene units according to isoprene rules [20] .…”