95124-24-6Relevant academic research and scientific papers
Application of Diazaphospholidine/Diazaphospholene-Based Bisphosphines in Room-Temperature Nickel-Catalyzed C(sp2)-N Cross-Couplings of Primary Alkylamines with (Hetero)aryl Chlorides and Bromides
Gatien, Alexandre V.,Lavoie, Christopher M.,Bennett, Raymond N.,Ferguson, Michael J.,McDonald, Robert,Johnson, Erin R.,Speed, Alexander W. H.,Stradiotto, Mark
, p. 5328 - 5339 (2018/05/14)
We report herein on the synthesis and catalytic application of a family of o-phenylene-bridged bisphosphine ancillary ligands featuring a bulky N-heterocyclic phosphine (NHP) donor fragment paired with an adjacent PR2 donor group (R = alkyl, aryl), whereby the incorporation of phosphorus into either a saturated or unsaturated heterocyclic ring serves as a means of modulating the donicity of the NHP fragment. Screening of these ancillary ligands in representative nickel-catalyzed C(sp2)-N cross-coupling test reactions allowed for the identification of one variant, featuring a saturated NHP structure and an adjacent diphenylphosphino donor group (i.e., NHP-DalPhos), as being particularly effective in reactions involving primary alkylamines. Notably, application of the derived precatalyst (NHP-DalPhos)NiCl(o-tolyl) (C1) enabled the typically challenging monoarylation of structurally diverse primary alkylamines with (hetero)aryl chlorides or bromides at room temperature. Also described are the results of our comparative density functional theory computational analysis of nickel-catalyzed primary alkylamine C(sp2)-N cross-couplings employing PAd-DalPhos or NHP-DalPhos.
Evaluating 1,1′-Bis(phosphino)ferrocene Ancillary Ligand Variants in the Nickel-Catalyzed C-N Cross-Coupling of (Hetero)aryl Chlorides
Clark, Jillian S. K.,Voth, Christopher N.,Ferguson, Michael J.,Stradiotto, Mark
, p. 679 - 686 (2017/04/21)
Previous reports in the literature have established the utility of 1,1′-bis(diphenylphosphino)ferrocene (DPPF, LPh) in the nickel-catalyzed cross-coupling of (hetero)aryl electrophiles with primary or secondary amines. In an effort to evaluate
A comparative reactivity survey of some prominent bisphosphine nickel(II) precatalysts in C-N cross-coupling
Clark, Jillian S. K.,Lavoie, Christopher M.,MacQueen, Preston M.,Ferguson, Michael J.,Stradiotto, Mark
supporting information, p. 3248 - 3254 (2016/10/09)
The synthesis and characterization of the new air-stable precatalyst (L1)Ni(o-tol)Cl (C1; where L1 = JosiPhos CyPF-Cy) is reported, along with the results of a comparative reactivity survey involving C1 and analogous PAd-DalPhos- and DPPF-containing precatalysts (C2 and C3, respectively) in representative nickel-catalyzed C(sp2)-N cross-coupling reactions. Precatalyst C1 was found to be competitive with, and in some cases complementary to, C2 in the monoarylation of ammonia and primary alkylamines with (hetero)aryl chlorides, including in otherwise challenging room temperature transformations. (Pseudo)halide comparison studies involving the cross-coupling of furfurylamine at room temperature revealed that in contrast to C2 precatalyst C1 performs less effectively with aryl bromides. Whereas C3 was found to be ineffective for such transformations, this DPPF-derived precatalyst proved superior to C1 and C2 in reactions involving the secondary dialkylamine test substrate morpholine.
Controlling first-row catalysts: Amination of aryl and heteroaryl chlorides and bromides with primary aliphatic amines catalyzed by a BINAP-ligated single-component Ni(0) complex
Ge, Shaozhong,Green, Rebecca A.,Hartwig, John F.
supporting information, p. 1617 - 1627 (2014/02/14)
First-row metal complexes often undergo undesirable one-electron redox processes during two-electron steps of catalytic cycles. We report the amination of aryl chlorides and bromides with primary aliphatic amines catalyzed by a well-defined, single-component nickel precursor (BINAP)Ni(η2-NC- Ph) (BINAP = 2,2′-bis(biphenylphosphino)-1,1′-binaphthalene) that minimizes the formation of Ni(I) species and (BINAP)2Ni. The scope of the reaction encompasses electronically varied aryl chlorides and nitrogen-containing heteroaryl chlorides, including pyridine, quinoline, and isoquinoline derivatives. Mechanistic studies support the catalytic cycle involving a Ni(0)/Ni(II) couple for this nickel-catalyzed amination and are inconsistent with a Ni(I) halide intermediate. Monitoring the reaction mixture by 31P NMR spectroscopy identified (BINAP)Ni(η2-NC-Ph) as the resting state of the catalyst in the amination of both aryl chlorides and bromides. Kinetic studies showed that the amination of aryl chlorides and bromides is first order in both catalyst and aryl halide and zero order in base and amine. The reaction of a representative aryl chloride is inverse first order in PhCN, but the reaction of a representative aryl bromide is zero order in PhCN. This difference in the order of the reaction in PhCN indicates that the aryl chloride reacts with (BINAP)Ni(0), formed by dissociation PhCN from (BINAP)Ni(η2-NC-Ph), but the aryl bromide directly reacts with (BINAP)Ni(η2-NC-Ph). The overall kinetic behavior is consistent with turnover-limiting oxidative addition of the aryl halide to Ni(0). Several pathways for catalyst decomposition were identified, such as the formation of the catalytically inactive bis(amine)-ligated arylnickel(II) chloride, (BINAP)2Ni(0), and the Ni(I) species [(BINAP)Ni(μ-Cl)] 2. By using a well-defined nickel complex as catalyst, the formation of (BINAP)2Ni(0) is avoided and the formation of the Ni(I) species [(BINAP)Ni(μ-Cl)]2 is minimized.
STUDIES IN THE FURAN SERIES. 22. N-ARYLFURFURYL- AND N-ARYL-5-METHYLFURFURYLAMINES AND THEIR N-ALLYL DERIVATIVES.
Klepo,Jakopcic
, p. 235 - 237 (2007/10/02)
The compounds, where aryl is a meta- or para-substituted chlorophenyl, methoxyphenyl, or methylphenyl group, were prepared by reduction of corresponding azomethines. Their allylation with allyl iodide or allyl bromide yielded tertiary N-arylfurfurylamines
