A Modular Approach for the Synthesis of Natural and Artificial Terpenoids

Angew Chem Int Ed Engl. 2023 Jul 13:e202307626. doi: 10.1002/anie.202307626. Online ahead of print.ABSTRACTMany terpenoids with isoprene unit(s) demonstrating critical biological activities have been isolated and characterized. Although there are natural and many artificial methods for their syntheses, there is a great demand for better understanding of the corresponding structure-activity relationship, efficiency, and diversity. In this work, 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 and the rhodium-catalyzed reaction of alkenyl boronates with 2,3-allenols yielding enals. This chem-stamp could easily be applied repeatedly and separately, empowering the modular concise syntheses of many natural and pharmaceutically active terpenoids including retinal, β-carotene, vitamin A, tretinoin, fenretinide, acitretin, ALRT1550, nigerapyrone C, peretinoin, and lycopene. Due 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, side chain, and two terminal groups.PMID:37439109 | DOI:10.1002/anie.202307626
Source: Angewandte Chemie - Category: Chemistry Authors: Source Type: research