50259-75-1

Upstream product

• 171819-59-3 4,4-Diphenyl-2-methyl-1-pyrrolidinol 
• 53001-06-2 2,2-diphenyl-4-pentenylamine 
• 947-91-1 Diphenylacetaldehyde 
• 126899-77-2 1,1-diphenyl-3-butene-1-carboxaldehyde 
• 1043416-22-3 CHF₃O₃S*C₁₇H₁₉N 
• 86-29-3 Diphenylacetonitrile 
• 5558-71-4 2,2-diphenyl-pent-4-enenitrile 
• 412277-08-8 5-amino-4,4-diphenyl-pentan-2-ol 

Downstream Products

• 1055301-00-2 (2-methyl-4,4-diphenylpyrrolidin-1-yl)(naphthalen-1′-yl)methanone 
• 1214263-63-4 C₁₇H₁₇N 
• 27357-20-6 5-methyl-3,3-diphenyl-pyrrolidin-2-one 

Relevant academic research and scientific papers

Synthesis, structure, and reactivity of tris(amidate) mono(amido) and tetrakis(amidate) complexes of group 4 transition metals

The syntheses of a series of tris(amidate) mono(amido) titanium and zirconium complexes are reported. The binding motif of the amidate ligand has been determined to depend on the size of the metal centre for these sterically demanding N,O-chelating ligands; the larger zirconium metal centre supports three κ2-(N,O) bound amidate ligands while the titanium analogue has one ligand bound in a κ1-(O) fashion to alleviate steric strain. Reactivity studies indicate that, despite high steric crowding about the tris(amidate) mono(amido) zirconium metal centre, transamination of the reactive dimethylamido ligand can be achieved using aniline. This complex is also an active precatalyst for intramolecular alkene hydroamination, in which protonolysis of one amidate ligand in the presence of excess amine is observed as an initiation step prior to catalytic turnover. Eight-coordinate homoleptic κ2-amidate complexes of zirconium and hafnium have also been prepared. This journal is The Royal Society of Chemistry 2013.

Synthesis and catalytic activity of tridentate N-(2-pyridylethyl)-substituted bulky amidinates of calcium and strontium

Metalation of the formamidine Dipp-N═C(H)-N(H)-C2H4-Py (1a) and benzamidine Dipp-N═C(Ph)-N(H)-C2H4-Py (1b) with [(thf)2M{N(SiMe3)2}2] (M = Ca, Sr) yields the corresponding homoleptic complexes [M{Dipp-N═C(R)-N-C2H4-Py}2] (M/R = Ca/H (2a), Ca/Ph (2b), and Sr/Ph (3b)) regardless of the applied stoichiometry. Only during calciation of Dipp-N═C(H)-N(H)-C2H4-Py (1a), the heteroleptic intermediate [{(Me3Si)2N}Ca{Dipp-N═C(R)-N-C2H4-Py}]2 (2a′) has been observed. The formamidinate complex of strontium crystallizes as a tmeda adduct of the type [(tmeda)Sr{Dipp-N═C(H)-N-C2H4-Py}2] (3a). Metalation of the pivalamidine Dipp-N═C(tBu)-N(H)-C2H4-Py (1c) leads to the formation of heteroleptic mononuclear [{(Me3Si)2N}M{Dipp-N═C(tBu)-N(H)-C2H4-Py}] (M = Ca (2c) and Sr (3c)) with a side-on bonding of the Dipp group to the alkaline earth metals. Calciation of chiral Dipp-N═C(tBu)-N(H)-CH2CH(Me)-Py (R)-1d and (S)-1d with [(thf)2Ca{N(SiMe3)2}2] yields the homoleptic complexes [Ca{Dipp-N═C(tBu)-N-CH2CH(Me)-Py}2] with the enantiomeric forms (R,R)-2d and (S,S)-2d regardless of the applied stoichiometry. The complexes 2c and 2d catalyze the intramolecular hydroamination of the aminoalkene 2,2-diphenylpent-4-enylamine yielding 2-methyl-4,4-diphenylpyrrolidine but the stereochemistry cannot be influenced by the chiral compounds (R,R)-2d and (S,S)-2d.

Experimental and Computational Studies of the Mechanisms of Hydroamination/Cyclisation of Unactivated α,ω-Amino-alkenes with CCC-NHC Pincer Zr Complexes

Four new CCC-NHC pincer Zr complexes have been synthesised, characterised, and used in mechanistic studies in the hydroamination/cyclisation of unactivated amino-alkenes. These Zr pre-catalysts will cyclise a primary amino-alkene, but no reaction was observed for a secondary amino-alkene even in the presence of a primary amine. The empirical rate law, experimentally determined activation parameters, and kinetic isotope effects (KIEs) are reported. Several possible mechanisms, including amido-versus imido-insertion and concerted-insertion versus [2+2] cycloaddition mechanisms, were modelled computationally at the PBEPBE level of theory with double-zeta quality basis sets. The formation of a catalytically relevant imido complex via the monoamido complexes was accompanied by in situ formation of ammonium salts of the substrates. The experimental and computational data are consistent with an imido-[2+2] cycloaddition mechanism for the CCC-NHC pincer diamido Zr complexes that follow saturation kinetics under catalytically relevant concentrations.

Synthesis and Reactivity of Indium(I) 1-Carba-closo-undecachlorododecaborate

The arene-solvated indium(I) species [In(C7H8)3][CHB11Cl11] (1) and [In(C6H5Br)1.5][CHB11Cl11] (2) were obtained by a redox reaction involving th

Synthesis and structural characterization of amido heteroscorpionate rare-earth metal complexes and hydroamination of aminoalkenes

The synthesis, characterization and fluxional behaviour of novel heteroscorpionate rare-earth (including the group 3 metals, scandium and yttrium) complexes are reported. The reaction of acetamide and thioacetamide heteroscorpionate protio-ligands pbptamH

Metal-pyrazole bifunction in half-sandwich C - N chelate iridium complexes: Pyrazole-pyrazolato interconversion and application to catalytic intramolecular hydroamination of aminoalkene

A study was conducted to demonstrate metal-pyrazole bifunction in half-sandwich C-N chelate iridium complexes, pyrazole-pyrazolato interconversion, and application to catalytic intramolecular hydroamination of aminoalkene. The chloro-pyrazole complex was obtained by acetate-promoted cyclometalation of 3,5-diphenylpyrazole and the 1H NMR spectrum exhibited a low-field NH singlet that disappeared upon treatment with D 2O. The Bronsted acidity of the coordinated pyrazole in the chloro-pyrazole complex was indicated by X-ray analysis, revealing the presence of intermolecular hydrogen bonds between the pyrazole proton and the chloro ligand. It was observed that the chloro-pyrazole complex underwent smooth dehydrochlorination with an equivalent amount of a base in toluene. Partial dehydrochlorination took place to afford the chloro-bridged pyrazolato-pyrazole complex when the chloro complex was treated with only 0.5 equiv of base.

Imido and amido titanium complexes that contain a [OSSO]-type bis(phenolato) ligand: Synthesis, structures, and hydroamination catalysis

Salt metathesis reaction of the imido complex [Ti(NR)-Cl 2(NC5H5)3] (R = tBu, C 6H3iPr2-2,6) with 1 equiv. of the lithium salt of the corresponding [OSSO]-type bis(phenol) [edtbp

Rare earth and alkaline earth metal complexes with Me2Si-bridged cyclopentadienyl-imidazolin-2-imine ligands and their use as constrained-geometry hydroamination catalysts

The imidazolin-2-imino-functionalized tetramethylcyclopentadiene, 3-H, has been prepared by the reaction of two equivalents of 1,3-diisopropyl-4,5- dimethylimidazolin-2-imine (1) with 5-(chlorodimethylsilyl)-1,2,3,4-tetramethyl- 1,3-cyclopentadiene (2). T

Optically active, bulky tris(oxazolinyl)borato magnesium and calcium compounds for asymmetric hydroamination/cyclization

The synthesis of the new chiral, pseudo C3-symmetric, monoanionic ligand tris(4S-tert-butyl-2-oxazolinyl)phenylborate [To T]- is reported. The steric bulk, tridentate coordination, and anionic charge of [ToT]su

Comparison of yttrium binaphthylamido alkyl and amide complexes for enantioselective intramolecular hydroamination

A chiral trisamido yttrium complex Y[(R)-C20H 12(NC5H9)2][NiPr2][THF] 2·LiCl coordinated by N-cyclopentyl binaphthylamine ligand has been prepared in situ and characterised by NM