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Molecular scaffolds endowed with all‐carbon quaternary stereocenter are ubiquitous in natural products and significant bioactive molecules. However, efficient construction of this type of structure units is full of challenge due to their congested chemical environment. Herein, we report a new gold(I) self‐relay catalysis merging [3,3]‐sigmatropic rearrangement/Nazarov cyclization with allylic alkylation...
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