Metal catalysed hydrovinylation

Abstract

An overview of the hydrovinylation reaction catalysed by transition metal organometallic complexes is given. The addition of ethylene to another CQC double bond of vinylarenes, dienes or strained olefins is highlighted as an elegant methodology to generate a new stereogenic centre. In addition, the introduction of a new vinyl group allows further functionalisation. The parameters that control the selectivity of the formal codimerisation reaction and some selected applications are discussed.

Asymmetric Hydrovinylation and Hydrogenation with Metal Complexes of C3‐Symmetric Tris‐Binaphthyl Monophosphites

“…However, when higher conversions were achieved, the isomerisation to 3phenyl-2-butenes increased ( Table 2, entries 2, 3 and 6, 7). [16][17][18] These results suggest that the adamantyl ester group at the ligand is the key feature that increases the stability of C 3 -symmetric helical structures [55] and/or might favour secondary interactions with palladium, thereby increasing the enantiodiscrimination (Scheme 3). [36] The enantioselectivity increased in the order Pd3 Ͻ Pd1 Ͻ Pd4 Ͻ Pd2 Ͻ Pd5, which does not match with the increasing bulkiness of the OR substituent at the phosphite ligand.…”

“…Chiral hemilabile ligands that have this bifunctional character have been demonstrated to advantageously influence the catalytic activity and selectivity in several asymmetric reactions, such as hydrovinylation [2][3][4] and hydrogenation of alkenes [5][6][7][8][9][10][11] among others. [16][17][18][19] This reaction, when applied to vinylarenes, is of great interest for enantioselective synthesis, be-gand with an adamantyl ester substituent led to 92 % ee toward (R)-3-phenyl-1-butene, which suggests that the ester functionality might provide a secondary hemilabile interaction with the metal, thus favouring the enantioselectivity control. [16][17][18][19] This reaction, when applied to vinylarenes, is of great interest for enantioselective synthesis, be-gand with an adamantyl ester substituent led to 92 % ee toward (R)-3-phenyl-1-butene, which suggests that the ester functionality might provide a secondary hemilabile interaction with the metal, thus favouring the enantioselectivity control.…”

“…Rhodium(I) complexes formed in situ with the same ligands were further applied in the hydrogenation of dimethyl itaconate, but gave limited activity. [16][17][18][19] Although some work on catalytic hydrovinylation has been carried out with cobalt [25,26] and ruthenium [27] complexes, nickel(II) [28][29][30][31][32][33] and palladium(II) [34][35][36][37][38] organometallic precursors modified with P-donor ligands are the most representative systems and they have been extensively studied. cause it provides a short route to enantiopure 2-arylpropionic acids.…”

1,4-Selective Hydrovinylation of Diene Catalyzed by an Iron Diimine Catalyst: A Computational Case Study on Two-State Reactivity

“…Carbon–carbon bond formation is one of the most important reactions in synthetic chemistry due to the insurmountable role of C–C bonds in organic molecules. Hydrovinylation represents an atom economical synthetic technique of C–C bond formation, combining multiple π-components by utilizing petrochemical feedstock, especially unactivated alkenes, − as substrates. Moreover, the structural isomerism of the resulting product opens up the possibility for regio- and stereoselective control and could further be utilized to construct other organic products with desired selectivities. ,, …”

Ruthenacyclopentanes as Intermediates in the Regio- and Stereoselective Linear Codimerization ofN-Vinylamides with Electron-Deficient Alkenes

“…Codimerization of alkenes is a promising, atom-efficient synthetic method that affords highly substituted alkenes with various functionalities from simple alkenes. − Thus far, Co, − Ni, − ,,− Ru, − Rh, ,,, Pd, − other transition-metal − complexes, and Lewis or Brønsted acids − have been used as catalysts for this r...…”