Synlett 2017; 28(13): 1586-1591
DOI: 10.1055/s-0036-1588806
letter
© Georg Thieme Verlag Stuttgart · New York

Thieme Chemistry Journals Awardees – Where Are They Now?
Efficient Cross-Coupling of Secondary Amines/Azoles and Activated (Hetero)Aryl Chlorides Using an Air-Stable DPEPhos/Nickel Pre-Catalyst

Ryan S. Sawatzky
a   Department of Chemistry, Dalhousie University, Halifax, Nova Scotia B3H 4R2, Canada   Email: mark.stradiotto@dal.ca
,
Michael J. Ferguson
b   X-ray Crystallography Laboratory, Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2, Canada
,
a   Department of Chemistry, Dalhousie University, Halifax, Nova Scotia B3H 4R2, Canada   Email: mark.stradiotto@dal.ca
› Author Affiliations
Supported by: Natural Sciences and Engineering Research Council of Canada (Discovery Grant RGPIN-2014-04807), (I2I Grant I2IPJ/485197-2015)
Further Information

Publication History

Received: 14 March 2017

Accepted after revision: 31 March 2017

Publication Date:
02 May 2017 (online)


Abstract

Synthesis and characterization of the new air-stable pre-catalyst (DPEPhos)Ni(2-mesityl)Br (C1) is reported, along with the application of this pre-catalyst in the cross-coupling of secondary amines/azoles with activated (hetero)aryl chlorides to afford tertiary (hetero)anilines. The performance of C1 in these cross-couplings is competitive with some of the best and/or most widely employed nickel catalysts for such transformations.

Supporting Information

 
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  • 19 CCDC 1534212 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures. See also the Supporting Information for details of the crystallographic analysis.
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  • 21 General Ligand-Screening Procedure for the Formation of Aryl Amines (Scheme [2]) In a nitrogen atmosphere glove box (TMEDA)Ni(o-tolyl)Cl (5 mol%, 0.015 mmol), ligand (7.5 mol%, 0.0225 mmol), LiOt-Bu (1.5 equiv, 0.45 mmol), 4-chlorobenzonitrile (1 equiv, 0.3 mmol), morpholine or indole (1.1 equiv, 0.33 mmol), and dry, degassed toluene (3 mL) were added to an oven-dried 1 dram vial containing a magnetic stir bar. The vial was sealed with a screw cap featuring a PTFE/silicone septum and removed from the glove box. The reaction mixture was magnetically stirred in a temperature-controlled aluminum heating block set to 110 °C for 16 h. The reaction mixture was then cooled to r.t. In air on the benchtop a 0.1 mL aliquot was taken, filtered, diluted with MeOH, and subjected to calibrated GC analysis.
  • 22 General Catalytic Procedure (Scheme [4]) In a nitrogen atmosphere glove box C1 (5 mol%, 0.05 mmol), phenylboronic acid (5 mol%, 0.015 mmol), LiOt-Bu (1.5 mmol), (hetero)aryl chloride (1 mmol), amine/azole (1.1 mmol), and dry, degassed toluene (10 mL) were added to an oven-dried 4 dram vial containing a magnetic stir bar. The vial was sealed with a screw cap featuring a PTFE/silicone septum and removed from the glove box. The reaction mixture was magnetically stirred in a temperature-controlled aluminum heating block set to 110 °C for 16 h (unoptimized). The reaction mixture was then cooled to r.t., taken up in EtOAc (ca. 30 mL) and washed with brine (3 × 50 mL). The organic layer was separated, dried over Na2SO4, filtered, and concentrated with the aid of a rotary evaporator to afford the crude product, which was purified via chromatographic methods (see the Supporting Information for complete details).
  • 23 Preparation of (L4)Ni(2-mesityl)Br (C1) Under nitrogen, NiBr2 (6.0 mmol, 1.3 g) was added to an oven-dried 100 mL, two-necked round-bottom flask equipped with a magnetic stir bar and a reflux condenser that had previously been evacuated and back-filled with nitrogen. Absolute EtOH (60 mL) was added, and the reaction mixture was sparged with nitrogen for 0.5 h. DPEPhos (L4, 6.0 mmol, 3.2 g) was added in one portion under positive pressure counterflow of nitrogen. The flask was sealed and heated at reflux (78 °C) for 0.5 h. The reaction mixture was then cooled to 0 °C in an ice bath and was subsequently subjected to suction filtration in air. The solids on the filter were washed with cold absolute EtOH (0 °C, 3 × 10 mL) and then Et2O (3 × 10 mL). The solid on the filter was then collected by dissolving/washing through with CH2Cl2; removal of the solvent from the collected CH2Cl2 eluent afforded a dark green solid (presumptively (L4)NiBr2, 4.3 g 94% yield), a portion of which was used subsequently without further purification in the synthesis of C1. Under nitrogen, (L4)NiBr2 (4.0 mmol, 3.0 g) and dry, degassed THF (40 mL) were added to an oven-dried 100 mL round-bottom flask equipped with a magnetic stir bar. The reaction mixture was cooled to 0 °C, stirring was initiated, and 2-mesitylmagnesium bromide (1 M in THF, 4.0 mmol, 3.9 mL) was added dropwise. Once the addition was complete, the reaction mixture was allowed to warm to r.t. over the course of 0.5 h. Subsequently the reaction flask was opened in air, and the THF was removed with the aid of a rotory evaporator. Cold MeOH (0 °C, 15 mL) was added, the reaction mixture was subjected to suction filtration, and the solids were washed with additional cold MeOH (0 °C, 3 × 15 mL) and hexanes (3 × 15 mL). The solid on the filter was then collected by dissolving/washing through with CH2Cl2; removal of the solvent from the collected CH2Cl2 eluent followed by extended drying in vacuo afforded C1 as a light orange powder (2.5 g, 79% yield). 1H NMR (300 MHz, CD2Cl2): δ = 7.95 (br s, 4 H), 7.72–7.63 (m, 1 H), 7.57–7.39 (br m, 7 H), 7.22–7.12 (br m, 3 H), 7.08–6.84 (br m, 5 H), 6.71–6.64 (m, 1 H), 6.55–6.47 (m, 1 H), 6.31–6.07 (br m, 4 H), 5.35–5.34 (m, 4 H), 2.54 (br s, 6 H), 2.16 (s, 3 H). 31P{1H} NMR (121.5 MHz, ­CD2Cl2): δ = 10.8 (d, J = 15 Hz), 5.5 (d, J = 15 Hz). Despite prolonged acquisition times satisfactory 13C{1H} NMR data could not be obtained for C1, owing both to hindered rotation that is apparent in the 1H NMR spectrum, and slow decomposition to paramagnetic byproducts upon standing in solution for extended periods. Anal. Calcd for C45H39O1P2Ni1Br1: C, 67.85; H, 4.94. Found: C, 67.49; H, 4.81. Crystals of C1 suitable for X-ray diffraction analysis were grown via slow evaporation of a CH2Cl2 solution.