The reactivity and the regioselective functionalization of silyl-diene enol ethers under a bifunctional organocatalyst provokes a dramatic change in the regioselectivity, from the 1,5- to the 1,3-functionalization. This variation makes possible the 1,3-addition of silyl-dienol ethers to nitroalkenes, giving access to the synthesis of tri- and tetrasubstituted double bonds in Rauhut-Currier type products. The process takes place under smooth conditions, nonanionic conditions, and with a high enantiomeric excess. A rational mechanistic pathway is presented based on DFT and mechanistic experiments.

In the Communication by J. Alemµn et al., the wrong journal was cited in reference [11i], the correct reference is included below. We apologize for this oversight.[11] i) C. Grondal, M. Jeanty, D. Enders, Nat. Chem.

We describe the unexpected behavior of the arylsulfonylacetylenes, which suffer an "anti-Michael" addition of organolithiums producing their alkynylation under very mild conditions. The broad scope, excellent yields, and simplicity of the experimental procedure are the main features of this methodology. A rational explanation of all these results can be achieved by theoretical calculations, which suggest that the association of the organolithiums to the electrophile is a previous step of their intramolecular attack and is responsible for the unexpected "anti-Michael" reactions observed for substituted sulfonylacetylenes.

Chameleon: a new strategy for the synthesis of a wide variety of alkynyl derivatives by the reaction of substituted arylsulfonylacetylenes with organolithium species is described. The high yields, the simplicity of the experimental procedure, the broad scope of this reaction, and the formation of C(sp)-C(sp2) bonds without using transition metals are the main features of this methodology.

Chamäleon: Eine neue Synthesestrategie für Alkinylderivate nutzt die Reaktion substituierter Arylsulfonylacetylene mit Organolithiumspezies (siehe Schema). Hohe Ausbeuten, eine große Substratbreite und der Verzicht auf Übergangsmetallverbindungen kennzeichnen diese leicht ausführbare CspC sp 2‐Verknüpfungsreaktion.