A series of enantioenriched fused bicyclic piperidines were accessed by a cycloisomerization /cycloaddition strategy. Starting from ynamide derivatives and aldehydes, good yields and high levels of stereoselectivity were obtained through sequential relay catalysis. The concurrent use of a gold complex with a diphenylprolinol silyl ether was applied to a combination of diversely functionalized substrates.

An enantioselective organocatalytic reaction of indole‐derived‐1‐azadienes with aldehydes leading the formation of enantioenriched cyclic N,O‐acetals is reported. The corresponding products can be obtained with high levels of stereoselectivity (de >95 %, 65–99 % ee, 8–98 % yield). Furthermore, fused tetracyclic scaffolds can also be obtained by implementing a one‐pot strategy involving an additional oxa‐Michael reaction from aldehydes bearing an α,β‐unsaturated ketone group.

The inside cover picture, designed by Fabrice Goursaud, holder of a PhD in organic chemistry and recently graduated from art school, illustrates the stereoselective synthesis of tetrahydro[2,3‐b]pyridine frameworks via one‐pot metal‐organo relay catalysis. The strategy, which involves a gold‐catalyzed cycloisomerization and a chiral amine mediated cycloaddition reaction, provides the targeted molecules in yields ranging from 27 to 90% and high levels of stereoselectivity (de>95%, 93–99% ee). Details can be found in the Communication by Manon Genet, Abdelilah Takfaoui, Jérôme Marrot, Christine Greck and Xavier Moreau. (M. Genet, A. Takfaoui, J. Marrot, C. Greck, X. Moreau, Adv. Synth. Catal. 2021, 363, 4516–4520; DOI: 10.1002/adsc.202100756).