The regioselective functionalization of terminal alkenes and alkynes is of utmost importance for the synthesis of a wide variety of organic products. Based on the original observation by Vladimir Markovnikov-the pioneer of this field of research-in the 19th century, the possible regioisomeric products are classified as Markovnikov or anti-Markovnikov products. Contrary to traditional belief, it is nowadays possible to control the regiochemistry of various additions of nucleophiles to alkenes and alkynes by applying different transition-metal catalysts. Recent developments in this area of selective functionalization of alkenes and alkynes are reviewed.

The field of asymmetric organocatalysis is rapidly developing and attracts an increasing number of research groups around the world. Here we present a brief overview of this area, guided by a mechanistic classification. Accordingly, organocatalysts are categorized as either Lewis base, Lewis acid, Brønsted base, or Brønsted acid catalysts.

A catalytic asymmetric Pictet-Spengler reaction has been developed, wherein treating substituted tryptamines with an aldehyde in the presence of a catalytic amount of a chiral phosphoric acid provides the corresponding tetrahydro-beta-carboline derivatives in high yields and enantiomeric excesses. The reaction works well with both aliphatic and aromatic aldehydes.

The base‐catalyzed hydroamination of olefins offers a simple and elegant access to various primary, secondary, and tertiary amines. Particular focus is placed on developments in the area of hydroamination of non‐activated olefins. Advantages and disadvantages of the methodology compared to other synthetic methods are presented. Special attention is paid to potential industrial applications of this chemistry.

Reaktionen zur selektiven Veredelung von Alkenen zählen zu den wichtigsten Methoden in der Organischen Synthese. Durch die Entwicklung von Übergangsmetallkatalysatoren in den letzten Jahrzehnten können heute alle Arten von Selektivität bei einer Vielzahl von Transformationen effizient gesteuert werden. Auch 100 Jahre nach dem Tod von Vladimir Markownikow – dem Pionier auf diesem Gebiet – ist die regioselektive Funktionalisierung von Alkenen und Alkinen immer noch ein wichtiges Forschungsziel: Besonders die Anti‐Markownikow‐Addition von Sauerstoff‐ und Stickstoff‐Nucleophilen an aliphatische Alkene und Alkine verfügt über großes industrielles Potenzial. In diesem Aufsatz werden neuere Entwicklungen auf diesem Gebiet beschrieben. Eine Auswahl aktueller Beispiele zeigt, wie die Regioselektivität durch die Wahl des Katalysators gesteuert werden kann.