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1H NMR (200 MHz, CDCl3): d=7.98 (dd, JHH =8.1, 1.2 Hz, 1H), 7.71–
and 4-chlorophenyl triflate (4a) (130 mg, 0.5 mmol) at 1208C in
4 mL of NMP. After combining two identical 0.5 mmol scale reac-
tions, compound 5 fa was isolated as a colourless solid (86 mg,
7.58 (m, 1H), 7.53 (dd, 3JHH =7.7, 1.6 Hz, 1H), 7.49–7.39 (m,1H),
7.25–7.14 (m, 2H), 7.14–6.99 (m, 1H), 6.61 (d, 3JHH =7.3 Hz, 1H),
6.03 (t, 3JHH =4.6 Hz, 1H), 2.91 (brs, 2H), 2.54–2.35 ppm (m, 3H);
13C NMR (101 MHz, CDCl3): d=149.2, 136.6, 135.9, 135.7, 134.2,
132.9, 132.4, 128.3, 128.0, 127.7, 127.4, 126.4, 124.23, 123.6, 27.8,
23.4 ppm; IR: n˜ =3072 (w), 3022 (w), 2930 (w), 2853 (w), 1516 (vs),
1489 (m), 1346 (vs), 1270 (m), 1152 (w), 1041 (w), 848 (m), 787 (s),
768 (s), 753 (vs), 738 cmÀ1 (vs). MS, m/z (%): 250 (36) [M+], 233 (31),
216 (19), 207 (19), 206 (100), 204 (17), 50 (17); elemental analysis:
calcd (%) for C16H13NO2 (251.29): C 76.48, H 5.21, N 5.57; found: C
76.30, H 5.35, N 5.69.
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31%). M.p. 97–988C; H NMR (400 MHz, CDCl3): d=7.89 (d, JHH
=
8.0 Hz, 1H), 7.82 (d, 3JHH =8.0 Hz, 1H), 7.77–7.72 (m, 1H), 7.53–
7.41 ppm (m, 4H); 13C NMR (101 MHz, CDCl3): d=137.7, 136.7,
134.9, 134.8, 130.8, 130.5, 128.9, 125.7, 125.2, 122.3, 117.1 ppm; IR:
n˜ =3058 (w), 1522 (w), 1486 (w), 1434 (w), 1400 (w), 1301 (w), 1251
(w), 1098 (w), 1012 (w), 984 (w), 899 (m), 828 (m), 820 (s), 750 cmÀ1
(vs); MS, m/z (%): 281 (13), 279 (81) [M+], 278 (100), 208 (19), 163
(8), 49 (6), 44 (6); elemental analysis: calcd (%) for C14H8Cl2S
(279.19): C 60.23, H 2.89, S 11.49; found: C 60.19, H 3.10, S 11.19.
4-Chloro-5’-methyl-2’-nitrobiphenyl (5ba): Compound 5ba was
prepared following the general procedure from potassium 5-
methyl-2-nitrobenzoate (3b) (164 mg, 0.75 mmol) and 4-chloro-
phenyl triflate (4a) (130 mg, 0.5 mmol) at 1008C in 4 mL of NMP.
After combining two identical 0.5 mmol scale reactions, com-
pound 5ba was isolated as a yellow oil (180 mg, 73%). The analyti-
cal data (NMR) matched those reported in the literature[14] [CAS:
70690-00-5].
Synthesis of palladium(0) complex 12
1,3-divinyl-1,1,3,3-tetramethyldisiloxane palladium(0) (11) in 2,4,6,8-
tetramethylcyclotetrasiloxane (1m, 250 mL, 250 mmol) was added to
a solution of L8 (102 mg, 250 mmol) in MeCN (8 mL). The solution
was stirred at RT for 16 h and a colourless solid formed. The solid
was filtered off and washed with MeCN (21 mL). The complex
was recrystallised from a solution of the crude product in Et2O
(0.5 mL) and MeCN (1.5 mL) at À208C yielding 12 as colourless
crystals (107 mg, 61%). M.p. 293–2948C (decomposed); 1H NMR
4,5’-Dichloro-2’-nitrobiphenyl (5ca): Compound 5ca was pre-
pared following the general procedure from potassium 5-chloro-2-
nitrobenzoate (3c) (180 mg, 0.75 mmol) and 4-chlorophenyl triflate
(4a) (130 mg, 0.5 mmol) at 1008C in 4 mL of NMP. After combining
two identical 0.5 mmol scale reactions, compound 5ca was isolat-
ed as a yellow solid (158 mg, 59%). M.p. 93–948C; 1H NMR
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(600 MHz, CDCl3): d=8.07 (d, JHH =5.0 Hz, 1H), 7.55 (dd, JHH =7.2,
4.3 Hz, 1H), 7.48 (t, 3JHH =7.5 Hz, 1H), 7.42 (t, 3JHH =8.2 Hz, 4H),
3
3
7.38–7.29 (m, 7H), 7.25 (t, JHH =7.8 Hz, 1H), 6.36 (d, JHH =5.0 Hz,
3
3
1H), 3.37 (brs, 2H), 3.14 (dd, JHH =16.1, 4.7 Hz, 2H), 2.84 (dd, JHH
=
3
3
(400 MHz, CDCl3): d=7.88 (d, JHH =8.8 Hz, 1H), 7.49 (dd, JHH =8.7,
2.4 Hz, 1H), 7.45–7.40 (m, 3H), 7.27–7.23 ppm (m, 2H); 13C NMR
(101 MHz, CDCl3): d=147.2, 138.7, 137.1, 135.0, 134.7, 131.8, 129.1,
129.1, 128.6, 125.8 ppm; IR: n˜ =3084 (w), 3053 (w), 2845 (w), 1605
(w), 1524 (s), 1509 (s), 1339 (vs), 1081 (m), 1012 (m), 859 (s), 829
(vs), 821 (vs), 799 (m), 756 cmÀ1 (s); MS, m/z (%): 268 (62) [M+], 267
(19), 266 (100), 238 (25), 232 (31), 175 (29), 150 (20); elemental
analysis: calcd (%) for C12H7Cl2NO2 (268.10): C 53.76, H 2.63, N 5.22;
found: C 53.90, H 2.76, N 5.19.
12.3, 6.5 Hz, 2H), 2.62–2.54 (m, 2H), 2.43 (brs, 2H), 1.81 (brs, 2H),
1.59 (brs, 2H), 0.23 (s, 6H), À0.23 ppm (s, 6H); 13C NMR (101 MHz,
1
CDCl3): d=167.1 (d, 3JCP =3.6 Hz), 159.1, 156.6, 144.4 (d, JCP
=
17.3 Hz), 138.6 (d, 1JCP =28.2 Hz), 134.9 (d. 2JCP =21.8 Hz), 134.8,
3
134.7, 132.9, 130.3 (d, 2JCP =6.4 Hz), 129.2, 128.8, 128.5 (d, JCP
=
4.5 Hz), 127.8, 127.7, 108.6, 68.6, 68.6, 66.8, 66.7, 45.9, 25.3, 1.4,
À1.2 ppm; 31P NMR (243 MHz, CDCl3): d=25.3 ppm; IR: n˜ =3051
(w), 3036 (w), 2957 (w), 2184 (w), 1569 (m), 1558 (m), 1543 (m),
1510 (m), 1478 (m), 1431 (w), 1339 (w), 1317 (m), 1247 (m), 1210
(w), 1090 (w), 998 (s), 837 (m), 781 (vs), 770 (vs), 740 cmÀ1 (s); ESI-
MS, m/z (%): 702 [M+H]+; elemental analysis: calcd (%) for
C34H42N3OPPdSi2 (733.35): C 58.15, H 6.03, N 5.98, found: C 58.20, H
4-Chloro-5’-methoxy-2’-nitrobiphenyl (5da): Compound 5da was
prepared following the general procedure from potassium 5-me-
thoxy-2-nitrobenzoate (3d) (176 mg, 0.75 mmol) and 4-chlorophen-
yl triflate (4a) (130 mg, 0.5 mmol) at 1008C in 4 mL of NMP. After
combining two identical 0.5 mmol scale reactions, compound 5da
was isolated as a yellow solid (184 mg, 70%, m.p. 118–1198C). The
analytical data (NMR, GC-MS) matched those reported in the litera-
ture[4a] [CAS: 911217-07-7].
5.94,
N
5.96. Crystal data for 12: C34H42N3OPPdSi2; M=
702.26 gmolÀ1
;
T=150(2) K; triclinic; P1; a=10.5752(3) , b=
¯
10.9336(4) , c=15.6717(6) ; a=89.765(3)8, b=88.537(3)8, g=
68.120(3)8;
V=1680.94(10) 3;
Z=2;
1calcd =1.387 mgmÀ1
;
m(MoKa)=0.702 mmÀ1 (l=0.71023 ); 18112 reflections collected;
independent reflections 9757; refinement converged to R=0.0324,
4-Chloro-4’,5’-dimethoxy-2’-nitrobiphenyl (5ea): Compound 5ea
was prepared following the general procedure from potassium 4,5-
dimethoxy-2-nitrobenzoate (3e) (199 mg, 0.75 mmol) and 4-chloro-
phenyl triflate (4a) (130 mg, 0.5 mmol) at 1008C in 4 mL of NMP.
After combining two identical 0.5 mmol scale reactions, compound
5ea was isolated as a yellow solid (220 mg, 75%). M.p. 146–1478C;
1H NMR (400 MHz, CDCl3): d=7.58 (s, 1H), 7.43–7.38 (m, 2H), 7.25–
7.20 (m, 2H), 6.74 (s, 1H), 4.00 (s, 3H), 3.96 ppm (s, 3H); 13C NMR
(101 MHz, CDCl3): d=152.4, 148.3, 140.8, 136.8, 134.0, 130.2, 129.4,
128.7, 113.4, 107.9, 45.5 ppm; IR: n˜ =3072 (w), 2962 (w), 2833 (w),
1498 (s), 1488 (vs), 1332 (s), 1282 (vs), 1268 (s), 1220 (vs), 1089 (s),
1023 (s), 1013 (m), 844 (s), 822 (m), 791 (vs), 757 cmÀ1 (m); MS, m/z
(%): 294 (31) [M+], 293 (16), 292 (100), 258 (18), 197 (13), 125 (13),
43 (62); elemental analysis: calcd (%) for C14H12ClNO4 (293.71): C
57.25, H 4.12, N 4.77; found: C 57.45, H 4.40, N 4.95.
wR2=0.0696 (I>2 s(I)), 429 Parameters and 12 restraints; min./
À3
max. residual electron density= +0.586 and À0.695 e
.
CCDC 1033628 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Acknowledgements
We thank the DFG (SFB-TRR 88 “3MET”) and the Stipendienstif-
tung Rheinland-Pfalz (fellowship to D. H.) for funding and Dr. K.
Gooßen for help with the preparation of the manuscript.
3-Chloro-2-(4’-chlorophenyl)benzo[b]thiophene (5 fa): Compound
5 fa was prepared following the general procedure from potassium
3-chlorobenzo[b]thiophene-2-carboxylate (3 f) (188 mg, 0.75 mmol)
Keywords: bridging ligands · carboxylic acids · copper · cross-
coupling · palladium
ChemCatChem 2015, 7, 3579 – 3588
3587
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