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R. S. Sawatzky et al.
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The
Cambridge
Crystallographic
Data
Centre
via
Information for details of the crystallographic analysis.
(20) Stradiotto, M. In New Trends in Cross-Coupling: Theory and
Application; Colacot, T. J., Ed.; Royal Society of Chemistry: Cam-
bridge, 2014, 228–253.
(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 evap-
orator to afford the crude product, which was purified via chro-
matographic methods (see the Supporting Information for com-
plete 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
(k) Nirmala,
M.;
Prakash,
G.;
Ramachandran,
R.;
Viswanathamurthi, P.; Malecki, J. G.; Linert, W. J. Mol. Catal. A:
Chem. 2015, 397, 56. (l) Magano, J.; Monfette, S. ACS Catal. 2015,
© Georg Thieme Verlag Stuttgart · New York — Synlett 2017, 28, A–F