1044276-57-4

Upstream product

• 24544-04-5 2,6-diisopropylbenzenamine 
• 583-53-9 2,3-dibromobenzene 
• 583-55-1 1-Bromo-2-iodobenzene 

Downstream Products

• 1234673-06-3 N¹,N^1’-(1,3-phenylene)bis(N²-(2,6-diisopropylphenyl)bezene-1,2-diamine) 
• 1263356-95-1 N-(2-(1H-imidazol-1-yl)phenyl)-2,6-diisopropylaniline 
• 599205-16-0 N-[2-(diphenylphosphino)phenyl]-2,6-diisopropylaniline 
• 1163303-79-4 N-(2-diisopropylphosphinophenyl)-2,6-diisopropylaniline 

Relevant academic research and scientific papers

Hydrosilylative Reduction of Tertiary Amides to Amines Catalyzed by N-(Phosphinoaryl)anilido Complexes of Iron and Cobalt

The synthesis and structural characterization of low-coordinate Fe(II) and Co(II) complexes supported by the monoanionic P,N-ligand N-(2-dicyclohexylphosphinophenyl)-2,6-diisopropylanilide are described. A three-coordinate (P,N)Fe-hexamethyldisilazide complex (2), and four-coordinate (P,N)Fe- (3-Fe) and (P,N)Co-alkyl (3-Co) complexes were evaluated as pre-catalysts for the hydrosilylative reduction of amides with PhSiH3 (5 mol % pre-catalyst, 1 equiv. PhSiH3, 80 °C, 1–24 h). The Fe complex 2 proved to be more broadly effective for the reduction of a variety of tertiary amide substrates, and was shown to mediate the reduction of N,N-dibenzylbenzamide at a loading of 1 mol %, to achieve near quantitative formation of tribenzylamine in 1 h (80 °C). Complex 2 also proved effective for the hydrosilylation of tertiary amides under ambient conditions (5 mol % Fe, 24 h), which is a unique example of room temperature amide hydrosilylation mediated by an Fe catalyst without the need for photochemical activation. Given the widespread use of amide reduction protocols in synthesis, the development of efficient Fe-based catalysts that operate under mild conditions is an important target.

Monoanionic bis(carbene) pincer complexes featuring cobalt(I-III) oxidation states

The synthesis and characterization of a series of cobalt complexes featuring a pincer bis(carbene) ligand of the meta-phenylene-bridged bis-N-heterocyclic carbene (ArCCC, Ar = 2,6-diispropylphenyl or mesityl) are reported. Cleavage of the aryl C-H bond of the ligand was achieved in a one-pot metalation procedure using Co(N(SiMe3)2)2(py)2, an equivalent of exogenous base, and trityl chloride to form the (DIPPCCC)CoCl2py complex. This species could be reduced to the Co(ii) and Co(i)-N2 molecules with the appropriate equivalents of reductant. Subsequent generation of (MesCCC)CoI-III derivatives with the mesityl ligand proceeded in good yields. A suite of characterization techniques and the interconversion between all three oxidation states of the cobalt complexes is described.

Amido phosphine complexes of zinc: Synthesis, structure, and catalytic ring-opening polymerization of ε-caprolactone

A series of diarylamido phosphine ligands of the type N-(2- dihydrocarbylphosphinophenyl)-2,6-dialkylanilide 1a-d have been prepared and employed to investigate the coordination chemistry of zinc. Protonolysis of ZnMe2 with one equivalent of N-(2-diphenylphosphinophenyl)-2,6- dimethylaniline (H[1a]) produced a mixture of [1a]ZnMe (2a) and Zn[1a] 2 (4a), whereas that involving ZnEt2 gave exclusively the three-coordinate [1a]ZnEt (3a). In contrast, treatment of ZnR2 (R = Me, Et) with N-(2-diphenylphosphinophenyl)-2,6-diisopropylaniline (H[1b]), N-(2-diisopropylphosphinophenyl)-2,6-dimethylaniline (H[1c]), or N-(2-diisopropylphosphinophenyl)-2,6-diisopropylaniline (H[1d]) under similar conditions generated quantitatively the corresponding three-coordinate zinc methyl 2b-d and zinc ethyl 3b-d. The bis-ligand complexes 4a,b,d were isolated by either protonolysis of alkyls 2-3 with one equivalent of H[1] or metathesis of ZnX2 (X = Cl, OAc) with the corresponding lithium derivatives 5. Attempts to prepare [1a-d]ZnX (X = Cl, OAc) were not successful regardless of stoichiometry of the starting materials employed. Alcoholysis of zinc alkyls 2-3 led undesirably to protonation on the amido nitrogen donor of 1, highlighting perhaps its higher basicity than alkyls. The reaction of ZnCl2 with H[1c] generated the phosphorus-bound adduct {H[1c]ZnCl(μ-Cl)}2 (6c). Interestingly, attempts to deprotonate 6c with n-BuLi produced unexpectedly the alkylated product [1c]Zn(n-Bu) (7c) instead of [1c]ZnCl; analogous reactions employing NEt3 led to Lewis base substitution to give H[1c] and [ZnCl2(NEt3)]2. Structural characterization of all new compounds was achieved by multi-nuclear NMR spectroscopy (1H, 13C, 31P, and 7Li) and X-ray crystallography (2c-d, 3c, 4d, 5c-d, and 6c) where appropriate. On the basis of the NMR and X-ray data, in combination with the synthetic investigations, the steric nature of these amido phosphine ligands is recognized to follow the order of 1a 1b 1c 1d. Interestingly, zinc alkyls 2-3 are all active initiators for catalytic ring-opening polymerization of ε-caprolactone whereas the bis-ligand complexes 4 are not.

Iridium complexes of CCC-pincer N-heterocyclic carbene ligands: Synthesis and catalytic C-H functionalization

A series of four meta-phenylene-bridged bis-benzimidazolium chlorides were synthesized as precursors to rigid, monoanionic, CCC-pincer N-heterocyclic carbene ligands. For ligands with mesityl, 3,5-xylyl, or 3,5-di-tert-butylphenyl side groups, reaction with [Ir(1,5-cyclooctadiene)Cl]2 in acetonitrile with either excess triethylamine or stoichiometric cesium fluoride as base gave neutral, iridium(III) pincer complexes of the formula Ir(CCC)HCl(MeCN), which were purified by chromatography on silica gel. Metalation failed under these conditions for a 2,6-diisopropylphenyl-substituted derivative. In combination with NaOtBu, these complexes form active catalysts for the acceptorless dehydrogenation of cyclooctane and for arene C-H borylation in neat arene solvent.

Novel benzo-and pyrido-anellated 1, 3-azaphospholes

We present the synthesis of OH-functional and bulky N-substituted benzazaphospholes, novel pyrido-azaphospholes, addition versus CH-metalation by tBuLi and reactions with electrophiles yielding a novel asymmetric P,N-heterocyclic ethylene-1,2-bis(phosphin