A bis(phosphinimino)methanide lanthanum amide as catalyst for the hydroamination/cyclisation, hydrosilylation and sequential hydroamination/hydrosilylation catalysis

[La[N(SiHMe2)2]2[CH(PPh2NSiMe3)2]], which was obtained via an amine elimination starting from [CH2(PPh2NSiMe3)2] and [La[N(SiHMe2)2]3(THF)2], was used as catalyst for the hydroamination/cyclisation, the hydrosilylation and the sequential hydroamination/hydrosilylation reaction.     

An in situ generated samarium complex as a practical catalyst for the efficient intramolecular hydroamination of non-activated alkenes

Mixing SmI₂ and NaN(TMS)₂ generates in situ an efficient catalyst that promotes the intramolecular hydroamination of non-activated olefins. A wide range of aminoolefins can be cyclised smoothly using this simple protocol. Mechanistic studies led to the identification of the putative active catalyst.     

Zirconium catalysed enantioselective hydroamination/cyclisation

A chiral zirconium alkyl cation catalyses the cyclisation of certain aminoalkenes with enantioselectivity up to 82%, the highest thus far observed for such a process.     

Chiral calcium catalysts for asymmetric hydroamination/cyclisation

Calcium complexes supported by chiral 1,2-diamines have been shown to be efficient catalysts for the asymmetric hydroamination of amino-olefin substrates; the calcium complexes [Ca(NN(R)){N(SiMe(3))(2)}(THF)] (R = (t)Bu, (i)Pr, Ph, 4-C(6)H(4)F) give enantioselectivities of up to 26% which marks a significant increase based upon literature precedence. The structure of [Ca(NN(Ph)){N(SiMe(3))(2)}(py)] has been computed with density functional methods.     

Intramolecular hydroamination/cyclisation of aminoallenes mediated by a neutral zirconocene catalyst: a computational mechanistic study

The complete catalytic cycle for the intramolecular hydroamination/cyclisation (IHC) of 4,5-hexadien-1-ylamine (1) by a prototypical [ZrCp(2)Me(2)] precatalyst (2) has been scrutinized by employing a reliable DFT method. The present study conducted by means of a detailed computational characterisation of structural and energetic aspects of alternative pathways for all of the relevant elementary steps complements the mechanistic insights revealed from experimental results. The operative mechanism entails an initial transformation of precatalyst 2 into the thermodynamically prevalent, but dormant, bis(amido)-Zr compound in the presence of aminoallene 1. This complex undergoes a reversible, rate-determining alpha-elimination of 1 to form the imidoallene-Zr complex. The substrate-free form, which contains a chelating imidoallene functionality, is the catalytically active species and is rapidly transformed into azazirconacyclobutane intermediates through a [2+2] cycloaddition reaction. This highly facile process does not proceed regioselectively because the alternative pathways for the formation of five- and six-membered azacycles have comparable probabilities. Degradation of cyclobutane intermediates by following the most feasible pathway occurs through protonolysis of the metallacycle moiety and subsequent proton transfer from the Zr-NHR moiety onto the azacycle. The five-membered allylamine is generated through protonation at carbon atom C(6) followed by alpha-hydrogen elimination, whereas protonolysis of the cyclobutane moiety at the Zr-N bond followed by proton transfer onto carbon atom C(5) is the dominant route for the six-membered product. Of the two consecutive proton transfer steps, the second one determines the overall kinetics of the entire protonation sequence. This process is predicted to be substantially slower than the cycloaddition reaction. The factors that regulate the composition of the cycloamine products have been elucidated.     

Intramolecular hydroamination/cyclisation of aminoallenes mediated by a cationic zirconocene catalyst: a computational mechanistic study

The complete sequence of steps of a tentative catalytic cycle for intramolecular hydroamination/cyclisation (IHC) of 4,5-hexadien-1-ylamine (1) by a prototypical cationic [Cp(2)ZrCH(3)](+) zirconocene precatalyst (2) has been examined by employing a gradient-corrected DFT method. The predicted smooth overall reaction energy profile is consistent with the available experimental data, thereby providing further confidence in the proposed mechanism. Following activation of the precatalyst by protonolytic cleavage of the Zr-Me bond, the catalytically active amidoallene-Zr complex undergoes addition of an allenic C[double bond, length as m-dash]C linkage across the Zr-N sigma-bond. The alternative exo- and endocyclic pathways show similar probabilities for the sterically less encumbered reactants {1 + 2} investigated herein. However, steric factors are expected to exert control on the regioselectivity of ring closure. On the other hand, the metathesis-type transition states for subsequent protonolysis are indicated to be less sensitive to steric demands. Formation of the six-membered azacycle-Zr intermediate through intramolecular C[double bond, length as m-dash]C insertion into the Zr-N sigma-bond is predicted to be turnover limiting. The factors that govern the regioselectivity of the aminoallene IHC have been elucidated.     

A chiral phenoxyamine magnesium catalyst for the enantioselective hydroamination/cyclization of aminoalkenes and intermolecular hydroamination of vinyl arenes

If Grignard had only known! A chiral magnesium complex catalyzes the intramolecular hydroamination/cyclization of aminoalkenes with high efficiency at temperatures as low as ?20?°C and enantioselectivities as high as 93?%?ee. The high activity of this system also allows the catalytic intermolecular anti-Markovnikov addition of pyrrolidine and benzylamine to vinyl arenes.     

Oxide surface-promoted Pd-complex catalysis for intramolecular O-activated alkene hydroamination: catalyst preparation, characterization, and performance

Supported Pd-P and Pd-N complexes prepared by a selective reaction of Pd-monomer precursors with SiO2, Al2O3 and TiO2 surfaces and characterized by EXAFS, XPS, XRF and gas analysis exhibited oxide surface-promoted catalysis for the catalytic intrahydroamination of 3-amino propanol vinyl ether to produce a cyclic amine.     

Kinetic resolution of chiral aminoalkenes via asymmetric hydroamination/cyclisation using binaphtholate yttrium complexes

Chiral binaphtholate yttrium aryl complexes are highly active and enantioselective catalysts for the asymmetric hydroamination of aminoalkenes, as well as the kinetic resolution of alpha-substituted 1-aminopent-4-enes to give trans-2,5-disubstituted pyrrolidines with good enantiomeric excess and high k(rel).     

Base-catalysed asymmetric hydroamination/cyclisation of aminoalkenes utilising a dimeric chiral diamidobinaphthyl dilithium salt

A dimeric proline derived diamidobinaphthyl dilithium salt represents the first example of a chiral main group metal based catalyst for asymmetric hydroamination/cyclisation reactions of aminoalkenes.     

Neutral versus cationic Group 3 metal alkyl catalysts: performance in intramolecular hydroamination/cyclisation

The relative catalytic activity of neutral dialkyl versus cationic monoalkyl Group 3 metal catalysts in the intramolecular hydroamination/cyclisation of the 2,2-dimethyl-4-pentenylamine reference substrate was investigated. This was found to depend strongly on the nature of the monoanionic ancillary ligand. With a bidentate amidinate ligand, the neutral catalysts were quite effective, but their cationic derivatives showed a much lower activity. The reaction kinetics suggest that this reflects an intrinsically higher activation barrier for the insertion of the olefinic moiety into the metal-amide bond for the cationic catalysts. In contrast, the neutral catalysts with tetradentate triamine-amide ligands showed a much lower activity than their cationic derivatives. It appears that this higher activity of the cationic triamine-amide catalysts reflects the beneficial effect of the additional available coordination space relative to the neutral species. The cationic triamine-amide yttrium catalysts are more active than the cationic amidinate catalysts of the same metal, possibly reflecting a stronger Y-amide bond in the latter, which is the more electron-deficient system.     

A highly regioselective Cu-exchanged tungstophosphoric acid catalyst for hydroarylation and hydroamination of alkynes

An efficient and reusable Cu-exchanged tungstophosphoric acid catalyst is demonstrated for the solvent free hydroarylation and hydroamination reactions of alkynes with numerous arene and amine derivatives, respectively. The catalyst exhibited exceptionally high activity and regioselectivity in both the reactions.     

Chiral-at-metal ruthenium complex as a metalloligand for asymmetric catalysis

The mononuclear [Ru(bpy)(2)(bpym)][PF(6)](2) complex (bpy = 2,2'-bipyridine; bpym = 2,2'-bipyrimidine) has been prepared in its enantiopure Lambda form. Because of the chelating property of the bipyrimidine moiety, it is possible to use this chiral-at-metal complex as a chiral inorganic ligand for a second metal cation acting as a catalytic center. Here we report the synthesis and the structural characterization of a novel dinuclear Lambda-[(bpy)(2)Ru(bpym)RuCl(p-cymene)](3+) compound (1). The asymmetric-inducing properties of the enantiopure chiral-at-metal metalloligand have been probed during asymmetric transfer hydrogenation to ketones catalyzed by 1. This provides one of the very few illustrations of the potential of this original class of chiral inorganic ligands.     

Intramolecular hydroamination catalysis using trans-N,N′-dibenzylcyclam zirconium complexes

The syntheses of (Bn₂Cyclam)Zr(NMe₂)₂ (1), (Bn₂Cyclam)Zr(NH^2,6-MePh)Cl (2) and (Bn₂Cyclam)Zr(N^2,6-MePh) (3) are described. The reactivity of 1, 3, (Bn₂Cyclam)Zr(CH₂Ph)₂ (4) and ((C₆H₄CH₂)₂Cyclam)Zr (5) as hydroamination catalysts of aminoalkenes is reported. High conversions of the primary gem-disubstituted aminoalkenes in 5- or 6-member ring N-heterocycles were observed. Reactions of 1, 4 and 5 with CH₂CHCH₂CPh₂CH₂NH₂ gave (Bn₂Cyclam)Zr(NHR)₂ (6) (R = CH₂CPh₂CH₂CHCH₂) that on heating converts sequentially into the mono-ortho-metallated species ((C₆H₄CH₂)BnCyclam)Zr(NHR) (7) and the bis-ortho-metallated ((C₆H₄CH₂)₂Cyclam)Zr (5), simultaneously with the hydroamination product.     

A new vanadium Schiff base complex as catalyst for oxidation of alcohols

The monoanionic bidentate Schiff base, N-(phenolyl)-benzaldimine (HL), has been employed to synthesize a new vanadium(IV) complex of general composition [VO(L)₂] (where L?=?O,?N donor of Schiff base). The ligand and complex have been fully characterized by elemental analyses, molar conductance data, FT-IR, ¹H- and ¹³C-NMR, and UV-Vis spectroscopies. Oxidation of alcohols to their corresponding aldehydes and ketones was conducted by this complex catalyst using Oxone as oxidant under biphasic reaction conditions (CH₂Cl₂/H₂O) and tetra-n-butylammonium bromide as phase transfer agent under air at room temperature.     

Intermolecular hydroamination of vinyl arenes using tungstophosphoric acid as a simple and efficient catalyst

The intermolecular hydroamination of vinyl arene derivatives has been efficiently carried out using a tungstophosphoric acid (TPA) catalyst under solvent free and mild reaction conditions. The present protocol provides an environmentally benign, easy to handle and highly active solid acid catalyst for hydroamination of vinyl arenes. The catalyst yields both hydroamination and hydroarylation products and the selectivity mostly depends on the reaction conditions.     

One-pot nitro-Mannich/hydroamination cascades for the direct synthesis of 2,5-disubstituted pyrroles using base and gold catalysis

An efficient, easy to perform, one-pot reaction cascade for the synthesis of 2,5-disubstituted pyrroles from p-toluenesulfonyl protected imines and 4-nitrobut-1-yne under a combination of base and gold(III) catalysis is reported.     

Merging homogeneous catalysis with biocatalysis; papain as hydrogenation catalyst

Papain, modified at Cys-25 with a monodentate phosphite ligand and complexed with Rh(COD)2BF4, is an active catalyst in the hydrogenation of methyl 2-acetamidoacrylate.