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

Abstract

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(η(2)-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 (31)P NMR spectroscopy identified (BINAP)Ni(η(2)-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(η(2)-NC-Ph), but the aryl bromide directly reacts with (BINAP)Ni(η(2)-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.

Scheme 1. Methods for Nickel-Catalyzed C–N Coupling Reactions

Scheme 2

Figure 1

Molecular structure of the nickelacyclic compound 9. All the ellipsoids are drawn at the 50% probability and all the hydrogen atoms are omitted for clarity.

Scheme 3

Scheme 4

Scheme 5

Figure 2

Plots of initial rates vs concentration of catalyst, aryl chloride, and benzonitrile for the amination of 4-chlorobenzotrifluoride (0.10–1.0 M) with n-octylamine (0.30 M) catalyzed by (BINAP)NiCl(C₆H₄-4-CF₃) (0.0060–0.018 M) in the presence of benzonitrile (0.090–0.180 M) and NaO^tBu (0.30 M) at room temperature.

Figure 3

Plots of initial rates vs concentration of catalyst, aryl bromide, and benzonitrile for the amination of 4-bromobenzotrifluoride (0.10–0.80 M) with n-octylamine (0.30 M) catalyzed by (BINAP)NiCl(C₆H₄-4-CF₃) (0.0060–0.018 M) in the presence of benzonitrile (0.090–0.180 M) and NaO^tBu (0.30 M) at room temperature.

Scheme 6. Proposed Catalytic Cycle for the Nickel-Catalyzed Amination of Aryl Chlorides and Bromides

Scheme 7