Transition metal catalysis is a useful tool for C−C bond‐forming reactions. Of special interest is the hydroalkynylation reaction of alkynes, which provides a simple method for the synthesis of enynes representing interesting structural motifs in organic chemistry. So far, there are only a few examples of gold(I)‐catalyzed hydroalkynylation reactions. Herein, we were able to show experimentally that the gold(I)‐catalyzed hydroalkynylation of ynamides leads regio‐ and stereoselectively to the corresponding ynenamides, a rather unknown type of molecule. A wide range of products could be generated with yields up to 90 % and, in contrast to many other gold‐catalyzed alkyne dimerization reactions, alkyl groups are tolerated. Quantum chemical calculations and NMR labelling experiments reveal a mechanism via dual gold catalysis.

Gold-catalyzed reactions of conjugated haloacetylenes are well known and usually result in the formation of addition or dimerization products. Herein, we report a gold-catalyzed reaction of non-conjugated­ haloacetylenes, which leads exclusively to the halogenated cyclization products. Remarkable is the gold-catalyzed reaction of tritylhaloacetylenes to haloindene derivatives, as mechanistic studies reveal that an 1,2-aryl shift occurs in the initially formed gold complex. The potential functionalization at the halogen atom and the wide scope of these cyclization reactions make them an attractive method for the construction of cyclic systems.

The Front Cover illustrates the gold(I)‐catalyzed hydroalkynylation of ynamides, which results in the stereo‐ and regioselective formation of ynenamides. By highlighting gold in the periodic table of elements and showing the structure of the dual gold catalyst in the background, we wanted to draw special interest to gold catalysis as a fascinating tool for the synthesis of complex molecules. Cover design by Enya Scheller. More information can be found in the Research Article by G. Haberhauer et al.

The determination of nanometer‐scale distances in solution is an enormous challenge. In their Research Article (e202301465) Gebhard Haberhauer and co‐workers demonstrate that distances in macrocycles can be measured using a molecular spring and 13C‐NMR spectroscopy. The sensitivity of the method even allows the determination of thermoelasticity at the molecular level: One studied system expands at low temperatures and shrinks at high temperatures.

For a molecular system, size and shape are of elementary importance for its function and properties. Therefore, the determination of distances within a molecule is essential. However, the commonly used methods are only suitable for distances smaller than 4 Å or larger than 15 Å. Here, we show that by incorporating a molecular spring, we can measure distances in macrocycles in the range of 10 Å using 13 C NMR spectroscopy. The accuracy of the method also allows to determine the temperature dependence of the distances. In one case, we find a contraction of the length by almost 10 % upon heating. This shrinking due to heating can be considered as inverse thermoelasticity at the molecular level and is a previously completely overlooked phenomenon that can be used in the future as a tool to change the length and, thus, the function of a system.