Hydrophosphinations nickel

Metal complex chemistry, homogeneous catalysis and phosphane chemistry have always been strongly connected, since phosphanes constitute one of the most important families of ligands. The catalytic addition of P(III)-H or P(IV)-H to unsaturated compounds (alkene, alkyne) offers an access to new phosphines with a good control of the regio- and stereoselectivity [98]. Hydrophosphination of terminal nonfunctional alkynes has already been reported with lanthanides [99, 100], or palladium and nickel catalysts [101]. Ruthenium catalysts have made possible the hydrophosphination of functional alkynes, thereby opening the way to the direct synthesis of bidentate ligands (Scheme 8.35) [102]. 

Scheme 33 Proposed mechanism for nickel-catalyzed asymmetric hydrophosphination via attack on a methacrylonitrile complex...

Scheme 34 Proposed mechanism for nickel- or palladium-catalyzed hydrophosphination via attack on a complex of an electron-rich alkene...

For example, a chiral nickel Lewis acid catalyst bound methacrylonitrile and activated it for nucleophilic attack by a secondary phosphine. Subsequent proton transfer resulted in enantioselective hydrophosphination (Scheme 33) [53, 54],... 

Enantioselective Nickel-Catalysed Hydrovinylation, Hydrophosphination, Hydrocyanation, and Hydroalkynylation Reactions ofAlkenes... 

Hydrophosphination of methacrylonitrile with an in situ generated nickel catalyst derived from the trisphosphine Pigiphos ligand. 

Example 4.15 Nickel-Catalyzed Hydrophosphination of Styrene Derivatives [56],... 

Sadow AD, Haller I, Fadini L, Togni A. Nickel(II)-catalyzed highly enantioselective hydrophosphination of methacryloni-trile. J. Am. Chem. Soc. 2004 126 14704-14705. 

Hoye PAT, Pringle PG, Smith MB, Worboys K (1993) Hydrophosphination of formaldehyde catalysed by tris-(hydroxymethyl)phosphine complexes of platinum, palladium or nickel. J Chem Soc Dalton Trans 269-274... 

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