Intermolecular Carbophosphination of Alkynes with Phosphole Oxides via Ni-Al Bimetal-Catalyzed C-P Bond Activation.

Intermolecular carbophosphination reaction of alkynes or alkenes with unreactive C-P bonds remains an elusive challenge. Herein, we used a Ni-Al bimetallic catalyst to realize an intermolecular carbophosphination reaction of alkynes with 5-membered phosphole oxides, providing a series of 7-membered phosphepines in up to 94 % yield.

Ag-NHC Complexes in the π-Activation of Alkynes.

Silver-NHC (NHC = N-heterocyclic carbene) complexes play a special role in the field of transition-metal complexes due to (1) their prominent biological activity, and (2) their critical role as transfer reagents for the synthesis of metal-NHC complexes by transmetalation. However, the application of silver-NHCs in catalysis is underdeveloped, particularly when compared to their group 11 counterparts, gold-NHCs (Au-NHC) and copper-NHCs (Cu-NHC). In this Special Issue on Featured Reviews in Organometallic Chemistry, we present a comprehensive overview of the application of silver-NHC complexes in the p-activation of alkynes. The functionalization of alkynes is one of the most important processes in chemistry, and it is at the bedrock of organic synthesis. Recent studies show the significant promise of silver-NHC complexes as unique and highly selective catalysts in this class of reactions. The review covers p-activation reactions catalyzed by Ag-NHCs since 2005 (the first example of p-activation in catalysis by Ag-NHCs) through December 2022. The review focuses on the structure of NHC ligands and p-functionalization methods, covering the following broadly defined topics: (1) intramolecular cyclizations; (2) CO2 fixation; and (3) hydrofunctionalization reactions. By discussing the role of Ag-NHC complexes in the p-functionalization of alkynes, the reader is provided with an overview of this important area of research and the role of Ag-NHCs to promote reactions that are beyond other group 11 metal-NHC complexes.

Synthetic Applications of Transition-Metal-Catalyzed C-P Bond Cleavage.

The wide occurrence of carbon-phosphorus bond activation in modern organic synthesis, catalyst deactivation, and biological process has attracted interest for synthetic applications. Over the past few decades, transition-metal-mediated transformations have become extremely powerful tools in organic synthesis. In this review, considerable progress that has been made in catalytic activations and transformations of carbon-phosphorus bonds within the coordination sphere of transition metals is described. Mechanistic information is also presented, and it is hoped that this review not only provides an account of the state of the art in the field, but also highlights the future potential of these reactions in organic synthesis.