Affiliation:
1. Research Center for Molecular Recognition and Synthesis Department of Chemistry Fudan University 220 Handan Lu Shanghai 200433 P. R. China
2. State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic Chemistry Chinese Academy of Sciences 345 Lingling Lu Shanghai 200032 P. R. China
Abstract
AbstractMany 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.
Funder
Key Technologies Research and Development Program
National Natural Science Foundation of China
Subject
General Chemistry,Catalysis
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