Gold‐Catalyzed Hydroarylation of Alkynes

Abstract

Hydroarylations, also called alkenylations of (hetero)arenes are important transformations in organic chemistry. The recent development of gold‐catalyzed processes to achieve such transformations has added a new tool in the chemist's toolbox. Thus, the hydroarylations of alkynes under gold catalysis are reviewed from a mechanistic and practical point of view. Both intramolecular and the more challenging intermolecular alkenylations are considered and described in a comprehensive account that includes detailed mechanisms as well as supporting theoretical calculations when relevant. This chapter also aims at illustrating the reactivity of internal and external alkynes which may differ in certain cases, as well as the various reactivities encountered with heteroarenes and arenes. The employment of supported gold catalysts to perform this type of transformations is also discussed in the last section of the chapter.

Construction of Medium-Sized Rings by Gold Catalysis

“…Gold complexes are also efficient catalysts in mediating hydroarylation processes, which involves addition of Ar–H across the alkynyl triple bond. Construction of medium-sized ring compounds through gold-catalyzed hydroarylation has been successfully employed in the synthesis of complex natural products.…”

Gold(I)‐Catalysed Hydroarylation of Lactam‐Derived Enynes as an Entry to Tetrahydrobenzo[g]quinolines

“…Intramolecular hydroarylation of alkynes (or alkenylation of arenes) is a valuable synthetic tool, alternative to Heck or cross‐coupling processes, to obtain alkenyl arenes. The recent and rapid advances of gold catalysis in this type of processes offer an easy access to an incredibly highly diversified array of cyclic systems Au(I) complexes are able to promote hydroarylation with a mechanism comparable to Friedel‐Crafts‐type electrophilic aromatic substitution, by employing the activated alkyne as electrophile. Carbocyclic polyaromatic compounds, oxygen, nitrogen, sulfur and phosphorus heterocyclic polyaromatic compounds have been successfully synthesized.…”

Unified Total Synthesis of Pyrroloazocine Indole Alkaloids Sheds Light on Their Biosynthetic Relationship

“…However, a synthetic approach to lapidilectine A-type natural compounds 3 – 5 has not yet been disclosed. Our interest in Kopsia indole alkaloids launched with the discovery of a gold-catalyzed hydroarylation of alkynes that allows a fast access to the pyrroloazocine indole core of these natural compounds . On the basis of this strategy, we developed a concise total synthesis of lundurines A–C …”