The extraordinary power of high‐pressure/solvent‐free conditions for the Diels–Alder reaction of thiophene has been established. For example, maleic anhydride (X=O) reacted with thiophene at 0.8 GPa and 100 °C to give the desired exo adduct in almost quantitative yield (see scheme). Further application of this method to maleimide (X=NR) and acrylic dienophiles demonstrated its remarkable potential.

For the first time, uncatalyzed, high‐pressure (0.6 GPa) reactions with ketones have proven to be a powerful way to perform the three‐component Strecker synthesis of α‐amino nitriles in high yields. Two types of double Strecker reactions were achieved, but attempts to perform triple Strecker reactions were unsuccessful.

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Druck gemacht! Diels‐Alder‐Reaktionen mit Thiophen wurden unter Hochdruck und lösungsmittelfreien Bedingungen durchgeführt. Beispielsweise reagierte Maleinsäureanhydrid (X=O) mit Thiophen bei 0.8 GPa und 100 °C fast quantitativ zum gewünschten exo‐Addukt (siehe Schema). Weitere Reaktionen unter diesen Bedingungen mit Maleinimid‐ (X=NR) und Acryl‐Dienophilen belegen das Potenzial dieser Methode.

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H i g h P r e s s u r e -P r o m o t e d U n c a t a l y z e d C y a n a t i o n o f A c e t a l s Abstract: A new uncatalyzed method for the preparation of cyanohydrin O-alkyl ethers was developed using the high-pressurepromoted reaction of acetals with trimethylsilyl cyanide in nitromethane.