Asymmetric hydroamination of non-activated carbon–carbon multiple bonds

Abstract

The catalysed enantioselective formation of carbon-nitrogen bonds by the hydroamination reaction is reviewed. All examples deal with substrates containing non-activated carbon-carbon multiple bonds which are transformed either via intramolecular or intermolecular reactions. Structurally different complexes already provided nitrogen containing compounds/heterocycles with high enantioselectivities.

Catalytic Hydroaminoalkylation

“…Protonolysis by the amine regenerates the starting bis(amide) and liberates the product. [17] Hydroaminoalkylations of a alkenes with N-alkyl arylamines were also reported [17] by using the closely related chlorotantalum anilide [ 2 Zr-(NMe 2 ) 2 ] (Ind = indenyl). [18] As these complexes also catalyze the hydroamination reaction, the authors tried to suppress that reaction pathway by using substrates that are unfavorable for the hydroamination reaction.…”

“…This catalytic conversion has attracted the interest of several research groups over the last decade. [1][2][3][4][5][6][7][8] A number of metal catalysts can be employed for this transformation, including complexes based on lanthanoids, [6] Group 4 metals, [4] platinum metals, [7] and also lithium, calcium, and recently gold.[5] Depending on the catalytic system, either an activation of the C À C multiple bond or the N À H function of the substrate takes place.[1] Another route to generate amines is the hydroaminomethylation; that is, a hydroformylation combined with a reductive amination to give amines. [9,10] The addition of amine a C À H bonds to alkenes to form branched alkylamines (hydroaminoalkylation) has been investigated recently by several research groups (Scheme 1).…”

Hydroamination reactions by metal triflates: Brønsted acid vs. metal catalysis?

“…Asymmetric 65 hydroamination reactions of unactivated alkenes have been limited almost exclusively to intramolecular cyclisation of aminoalkenes, 1,14 with some limited intermolecular examples involving the addition of anilines to norbornene and styrene, catalysed by iridium 34 and palladium, 35 respectively.…”

Asymmetric Hydroamination

“…Significant progress in this area has been made since 2003 utilizing noncyclopentadienyl-based ligand sets [5][6][7], thus avoiding configurational instability issues of the chiral lanthanocene complexes. However, while enantioselectivities have improved rather significantly, only few catalyst systems [52] display the same high catalytic activity as the lanthanocene catalysts.…”