The Palladium/Mor-DalPhos Catalyst System
FULL PAPER
mental analysis calcd (%) for C37H49PdCl1PNO2 (712.6372 gmolÀ1): C
62.34, H 6.93, N 1.97; found: C 62.44, H 6.86, N 1.72.
CH2Cl2/pentane (1:1, 3ꢂ2 mL) mixtures, forming a pale orange powder
that was dried in vacuo for several days to afford the desired compound
(containing 5.5% Et2O as observed by 1H NMR spectroscopy) in 90%
yield (184.7 mg, 0.270 mmol). 1H NMR (500.1 MHz, CDCl3): d=8.77 (d,
J=1.6 Hz, 1H; pyridyl H), 8.24 (ddd, J=8.4, 3.5, 0.9 Hz, 1H; ArH), 8.04
(dd, J=4.7, 1.5 Hz, 1H; pyridyl H), 7.85–7.80 (m, 2H; pyridyl+ArH),
7.67–7.64 (m, 1H; ArH), 7.43–7.40 (m, 1H; ArH), 6.93 (dd, J=7.8,
4.7 Hz, 1H; pyridyl H), 5.29–5.24 (m, 2H; morph CH2), 4.16–4.11 (m,
2H; morph CH2), 4.03–3.98 (m, 2H; morph CH2), 3.10–3.05 (m, 2H;
morph CH2), 2.26 (brs, 6H; 1-Ad CH2), 1.95 (brs, 12H; 1-Ad CH/CH2),
1.67 ppm (brs, 12H; 1-Ad CH2); 13C{1H} NMR (125.8 MHz, CDCl3): d=
160.4 (d, JPC =12.5 Hz; aryl Cquat), 157.0 (pyridyl CH), 146.4 (pyridyl
CH), 143.9 (pyridyl CH), 138.5 (pyridyl Cquat), 136.0 (aryl CH), 132.9
(aryl CH), 128.7 (d, JPC =7.8 Hz; aryl CH), 127.0 (d, JPC =29.5 Hz; aryl
Cquat), 126.2 (d, JPC =4.6 Hz; aryl CH), 122.7 (pyridyl CH), 61.9 (morph
CH2), 55.5 (morph CH2), 55.4 (morph CH2), 43.4–43.3 (m; 1-Ad Cquat),
40.8 (1-Ad CH2), 36.3 (1-Ad CH2), 28.6 ppm (d, JPC =9.3 Hz; 1-Ad CH);
31P{1H} NMR (202.5 MHz, CDCl3): d=61.9; elemental analysis calcd (%)
for C35H46ClN2OPPd (683.5993 gmolÀ1): C 61.49, H 6.78, N 4.10; found:
C 61.11, H 6.73, N 3.87.
[(k2-P, N-Mor-DalPhos)Pd
ACTHNUGRTENUNG(4-PhMe)Cl] (1c): Isolated as an off-white
solid in 66% yield (46.3 mg, 0.066 mmol). 1H NMR (500.1 MHz, CDCl3):
d=8.25–8.21 (m, 1H; ArH), 7.86–7.82 (m, 1H; ArH), 7.65–7.60 (m, 1H;
À
ArH), 7.40–7.37 (m, 3H; 2Pd-ArH, ArH), 6.83 (d, J=7.9 Hz, 2H; Pd
ArH), 5.29–5.23 (m, 2H; morph CH2), 4.15–4.11 (m, 2H; morph CH2),
4.02–3.97 (m, 2H; morph CH2), 3.06–3.01 (m, 2H; morph CH2), 2.31–
2.28 (m, 6H; 1-Ad CH2), 2.23 (s, 3H; ArCH3), 2.01–1.99 (m, 6H; 1-Ad
CH2), 1.95–1.94 (m, 6H; 1-Ad CH), 1.71–1.65 ppm (m, 12H; 1-Ad CH2);
13C{1H} NMR (125.8 MHz, CDCl3): d=160.5 (d, JPC =12.6 Hz; aryl Cquat),
À
À
138.3 (Pd aryl CH), 136.5 (Pd aryl Cquat), 136.1 (aryl CH), 132.5 (aryl
À
À
CH), 131.6 (Pd aryl Cquat), 128.8 (d, JPC =7.5 Hz; aryl CH), 127.7 (Pd
aryl CH), 127.5 (aryl Cquat), 126.9 (d, JPC =4.4 Hz; aryl CH), 62.0 (morph
CH2), 55.1 (morph CH2), 43.2 (d, JPC =14.2 Hz; 1-Ad Cquat), 40.7 (1-Ad
CH2), 36.4 (1-Ad CH2), 28.7 (d, JPC =9.4 Hz; 1-Ad CH), 21.0 ppm (Ar
CH3); 31P{1H} NMR (202.5 MHz, CDCl3): d=59.4; elemental analysis
calcd (%) for C37H49ClNOPPd (696.6378 gmolÀ1): C 63.79, H 7.09, N
2.01; found: C 63.58, H 6.89, N 1.92.
[(k2-P, N-Mor-DalPhos)Pd
ACTHNUGRTENUNG(2-PhMe)Cl] (1d): Isolated as a beige powder
[(k2-P, N-Mor-DalPhos)Pd(h1-cinnamyl)Cl] (2): A vial was charged with
Mor-DalPhos (139.1 mg, 0.300 mmol, 1.0 equiv), [{PdACHTUNTRGNE(UNG cinnamyl)Cl}2]
in 75% yield (52.4 mg, 0.075 mmol). 1H NMR (500.1 MHz, CDCl3): d=
8.23 (ddd, J=8.4, 3.6, 1.0 Hz, 1H; ArH), 7.89–7.86 (m, 1H; ArH), 7.65–
(77.7 mg, 0.300 mmol, 1.0 equiv), and THF (4 mL). The resulting clear
orange solution was stirred at room temperature for 1 h during which
time the reaction became cloudy and lighter in color, forming a milky
yellow solution. The presence of a new product (2) was confirmed by use
of 31P NMR techniques. The resulting slurry was concentrated to dryness,
washed with Et2O (5ꢂ2 mL) until the washings remained colorless, and
dried to afford the title compound as a yellow powder in 92% yield
(200 mg, 0.277 mmol). Crystals suitable for single-crystal X-ray diffrac-
tion analysis were obtained from vapour diffusion of hexanes into a di-
chloromethane/ethyl acetate solution of the title compound. 1H NMR
(500.1 MHz, CDCl3): d=7.89–7.83 (m, 2H; ArH), 7.73–7.71 (m, 2H; cin
Ph), 7.63–7.60 (m, 1H; ArH), 7.44–7.41 (m, 1H; ArH), 7.39–7.33 (m,
3H; cin Ph), 6.80 (dd, J=14.5, 8.8 Hz, 1H; alkenyl H), 6.42–6.36 (m, 1H;
alkenyl H), 3.86–3.81 (m, 2H; morph CH2), 3.74–3.68 (m, 2H; morph
À
7.61 (m, 1H; ArH), 7.54–7.52 (m, 1H; Pd ArH), 7.40–7.37 (m, 1H;
À
À
ArH), 6.91–6.88 (m, 1H; Pd ArH), 6.85–6.80 (m, 2H; Pd ArH), 5.33–
5.27 (m, 1H; morph CH2), 5.24–5.18 (m, 1H; morph CH2), 4.18–4.12 (m,
2H; morph CH2), 4.03–3.96 (m, 2H; morph CH2), 3.09–2.99 (m, 2H;
morph CH2), 2.87 (s, 3H; ArCH3), 2.45–2.43 (m, 3H; 1-Ad CH2), 2.13–
2.03 (m, 9H; 1-Ad CH/CH2), 1.86 (brs, 6H; 1-Ad CH/CH2), 1.79–1.71
(m, 6H; 1-Ad CH2), 1.66–1.59 ppm (m, 6H; 1-Ad CH2); 13C{1H} NMR
À
(125.8 MHz, CDCl3): d=160.3 (d, JPC =12.8 Hz; aryl Cquat), 142.4 (Pd
aryl Cquat), 142.0 (d, JPC =3.6 Hz; Pd aryl Cquat), 137.4 (d, JPC =2.7 Hz;
Pd aryl CH), 135.8 (aryl CH), 132.5 (aryl CH), 128.9 (d, JPC =7.3 Hz;
aryl CH), 128.6 (Pd aryl CH), 127.9 (d, JPC =28.2 Hz; aryl Cquat), 126.0
(d, JPC =4.2 Hz; aryl CH), 123.4 (Pd aryl CH), 123.1 (Pd aryl CH), 62.0
(morph CH2), 61.9 (morph CH2), 55.2 (morph CH2), 54.6 (morph CH2),
42.7 (d, JPC =15.1 Hz; 1-Ad Cquat), 42.5 (d, JPC =12.9 Hz; 1-Ad Cquat), 41.0
(1-Ad CH2), 39.7 (1-Ad CH2), 36.4 (1-Ad CH2), 36.3 (1-Ad CH2), 28.8
(Ar CH3), 28.8 (d, JPC =9.4 Hz; 1-Ad CH), 28.5 ppm (d, JPC =9.2 Hz; 1-
Ad CH); 31P{1H} NMR (202.5 MHz, CDCl3): d=58.3; elemental analysis
calcd (%) for C37H49ClNOPPd (696.6378 gmolÀ1): C 63.79, H 7.09, N
2.01; found: C 63.88, H 6.97, N 1.89.
À
À
À
À
À
À
CH2), 3.62–3.60 (m, 4H; Pd CH2/morph CH2), 3.14–3.10 (m, 2H; morph
CH2), 2.28–2.26 (m, 6H; 1-Ad CH2), 2.02 (brs, 6H; 1-Ad CH), 1.96–1.94
(m, 6H; 1-Ad CH2), 1.74–1.67 ppm (m, 12H; 1-Ad CH2); 13C{1H} NMR
(125.8 MHz, CDCl3): d=160.3 (d, JPC =14.1 Hz; aryl Cquat), 136.9 (d,
J
PC =6.3 Hz; Ph Cquat), 135.7 (aryl CH), 133.0 (aryl CH), 129.4 (Ph CH),
128.6 (aryl CH), 127.8 (Ph CH), 127.4 (d, JPC =28.9 Hz; aryl Cquat), 127.4
(aryl CH), 126.6 (d, JPC =7.6 Hz; aryl CH), 122.5 (d, JPC =17.4 Hz; alken-
yl CH), 114.5 (alkenyl CH), 65.0 (morph CH2), 58.5 (morph CH2), 43.0
(d, JPC =12.1 Hz; 1-Ad Cquat), 41.1 (1-Ad CH2), 36.2 (1-Ad CH2), 35.7
À
[(k2-P, N-Mor-DalPhos)Pd
ACTHUNTRGNE(NUG 4-PhCF3)Cl] (1e): Isolated as an off-white
powder in 80% yield (59.7 mg. 0.080 mmol). 1H NMR (500.1 MHz,
CDCl3): d=8.24 (dd, J=8.4, 3.1 Hz; ArH), 7.85–7.82 (m, 1H; ArH), 7.70
(d, J=7.8H, 2H; Pd-ArH), 7.67–7.64 (m, 1H; ArH), 7.41 (t, J=7.6 Hz;
(Pd CH2), 28.7 ppm (d,
J
PC =9.3 Hz; 1-Ad CH); 31P{1H} NMR
À
ArH), 7.21 (d, J=8.1 Hz, 2H; Pd ArH), 5.28–5.23 (m, 2H; morph CH2),
(202.5 MHz, CDCl3): d=75.4 ppm; elemental analysis calcd (%) for
C39H51ClNOPPd (722.6751 gmolÀ1): C 64.82, H 7.11, N 1.94; found: C
64.55, H 7.02, N 1.89.
[(k2-P, N-Mor-DalPhos)Pd(h3-cinnamyl)]OTf (3): Silver trifluoromethane-
4.16–4.11 (m, 2H; morph CH2), 4.03–3.98 (m, 2H; morph CH2), 3.09–
3.04 (m, 2H; morph CH2), 2.29–2.26 (m, 6H; 1-Ad CH2), 1.96 (brs, 12H;
1-Ad CH/CH2), 1.68 ppm (brs, 12H; 1-Ad CH2); 13C{1H} NMR
(125.8 MHz, CDCl3): d=160.4 (d, JPC =12.5 Hz; aryl Cquat), 149.3 (Pd
aryl Cquat), 138.7 (Pd aryl CH), 136.1 (aryl CH), 132.8 (aryl CH), 128.8
À
sulfonate (28.3 mg, 0.110 mmol, 1.1 equiv) was added to a vial containing
À
2
(72.3 mg, 0.100 mmol, 1.0 equiv) in CH2Cl2 (2 mL). The resulting
(d, J=7.6 Hz; aryl CH), 127.1 (d, JPC =29.1 Hz; aryl Cquat), 126.2 (d, JPC
=
yellow solution was stirred for ꢁ1 h, during which time a gray precipitate
formed. Reaction completion was determined by the presence of a single
new phosphorus-containing species, as observed by 31P NMR spectrosco-
py. The mixture was filtered over Celite and the filtrate was treated with
pentane (3 mL) to afford a yellow solid in solution, which in turn was
separated from the solvent and washed with pentane (2ꢂ3 mL). The
solid was dried to afford the title compound as a yellow powder in 98%
yield (81.6 mg, 0.098 mmol). Crystals suitable for single-crystal X-ray dif-
fraction analysis were obtained via slow evaporation of a CHCl3 solution
of the title compound. 1H NMR (500.1 MHz, CDCl3): d=7.90–7.84 (m,
2H; ArH), 7.79–7.77 (m, 2H; cin Ph), 7.67–7.64 (m, 1H; ArH), 7.48 (t,
À
4.6 Hz; aryl CH), 125.2 (JCF =270.7 Hz; CF3), 125.0 (JCF =31.8 Hz; Pd
À
aryl Cquat), 122.4 (Pd aryl CH), 61.9 (morph CH2), 55.4 (morph CH2),
43.4 (d, JPC =14.4 Hz; 1-Ad Cquat), 40.8 (1-Ad CH2), 36.3 (1-Ad CH2),
28.6 ppm (d, JPC =9.3 Hz; 1-Ad CH); 31P{1H} NMR (202.5 MHz, CDCl3):
d=60.5; elemental analysis calcd (%) for C37H46ClF3NOPPd
(750.6092 gmolÀ1): C 59.20, H 6.18, N 1.87; found: C 59.15, H 6.22, N
1.90.
[(k2-P, N-Mor-DalPhos)Pd(3-pyridyl)Cl] (1 f): Mor-DalPhos (46.4 mg,
0.100 mmol, 1.0 equiv), NaOtBu (34.6 mg, 0.360 mmol, 1.2 equiv), 3-
chloropyridine (1 mL), and THF (2 mL) were added to a vial containing
[{PdACHTUNGTRENNUNG(allyl)Cl}2] (57.6 mg, 0.158 mmol, 0.525 equiv). The resulting brown
J
PC =7.6 Hz, 1H; ArH), 7.46–7.42 (m, 3H; cin Ph), 6.32 (dd, J=14.1,
mixture was sealed, removed from the glovebox, and heated at 658C for
3 h, at which time complete consumption of the ligand was confirmed by
use of 31P NMR spectroscopy. The resulting slurry was concentrated to
dryness, dissolved in CH2Cl2 (2 mL) and filtered (removing insoluble im-
purities). The filtrate was triturated with CH2Cl2/Et2O (1:1, 2ꢂ2 mL) and
9.8 Hz, 1H; allyl CH), 6.21–6.15 (m, 1H; allyl CH), 4.05 (d, J=5.5 Hz,
1H; allyl CH), 4.00–3.92 (m, 2H; morph CH2), 3.63–3.61 (m, 1H; morph
CH2), 3.46–3.43 (m, 1H; morph CH2), 3.32–3.22 (m, 2H; morph CH2),
3.13–3.09 (m, 1H; allyl CH), 3.02–2.94 (m, 2H; morph CH2), 2.30–2.27
(m, 3H; 1-Ad CH2), 2.08–1.97 (m, 12H; 1-Ad CH/CH2), 1.84 (brs, 3H;
Chem. Eur. J. 2013, 00, 0 – 0
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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