Organophosphorus and Iron Catalysis: Good Partners for Hydrometalation of Olefins and Alkynes

Abstract

The last decades have seen an impressive development of iron complexes involving organophosphorus ligands applied in homogeneous catalyzed hydrometalation of olefins and alkynes. Two main topics will be covered in this JOCSynopsis: (i) an overview of the achievements in the area of iron-catalyzed hydrophosphination and then (ii) hydrosilylation, hydroborylation, and hydromagnesiation reactions promoted by catalysts based on organophosphorus ligands and iron.

Hydroelementation of diynes

“…[332][333][334]339 The synthesis of vinylicphoshpines can be carried out using the hydrophosphination reaction. 30,59,346 This type of addition reaction was also used in the reaction with conjugated and separated diynes, but, unlike hydroamination, the examples are limited only to a few papers.…”

“…Over the last few decades, several reviews have been published focusing on this subject. 14,17,18,22,25,30,[48][49][50][51][52][53][54][55][56][57][58][59][60][61] Particularly useful are hydroboration, hydrosilylation, hydroamination, hydrophosphination, and hydrostannation processes, which lead to important building blocks in organic and materials chemistry. Although many different terminal and internal alkynes have been used in these transformations, literature focused on the hydroelementation of conjugated or separated diynes is much rarer and has never been collated in a review before.…”

Recent Advances in Nonprecious Metal Catalysis

“…The examples include hydrogenation, transfer hydrogenation, and hydrosilylation of various unsaturated compounds, including olefins, alkynes, carbonyl and carboxylic derivatives, imines, nitro compounds, and sulfoxides. Most recently, they provided an overview in the area of iron-catalyzed hydrometalation of alkenes and alkynes . That review covered two main topics: Fe-catalyzed hydrophosphination and hydrosilylation, hydroborylation, and hydromagnesiation reactions promoted by combination of the Fe catalyst with organophosphorus ligands (e.g., arylphosphines).…”

“…Most recently, they provided an overview in the area of iron-catalyzed hydrometalation of alkenes and alkynes. 87 That review covered two main topics: Fecatalyzed hydrophosphination and hydrosilylation, hydroborylation, and hydromagnesiation reactions promoted by combination of the Fe catalyst with organophosphorus ligands (e.g., arylphosphines).…”

Copper-Catalyzed Regiodivergent Borylation of Fluorinated Alkynes and Palladium-Catalyzed Regiospecific Suzuki–Miyaura Cross-Coupling

“…2 Hydrometalation reactions are key transformations in modern organic synthesis, used to control stereoselectivity depending on the reaction conditions, and in the concomitant installation of a metal or metalloid for further functionalizations. 3 Several reports on the hydrometalation of R f -alkynes have appeared in the literature; these reactions include hydrostannylations, hydrosilylations, hydrogermy-lations, hydroborations, hydrocuprations, and hydroaluminations (Schemes 1a-c). 4 Surprisingly, in all these methods, the major product is formed with the introduction of the metal/metalloid (M) on the carbon atom  to the CF 3 group…”