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on F2 1.395; D1max =0.274 eꢂÀ3. CCDC 1031901 contains the sup-
plementary crystallographic data for this paper. These data can be
obtained free of charge from the Cambridge Crystallographic Data
Compound 2
A solution of 12 (0.35 g, 0.34 mmol) in toluene (15 mL) was treated
with 19 (0.13 g, 0.51 mmol), and then stirred at 1108C under
argon. Triethylamine (0.051 g, 0.51 mmol) was dissolved in toluene
(2.0 mL) and slowly added with a syringe pump. The reaction was
stirred and heated at reflux for 21 h. After the reaction was com-
plete, the solvent was removed under reduced pressure. Subse-
quently, water (100 mL) was added and the suspension was ex-
tracted with CH2Cl2 (3ꢁ100 mL). The organic layer was dried over
anhydrous MgSO4 and the solvent was removed under reduced
pressure to afford the crude reaction mixture, which was purified
by column chromatography on silica gel (ethyl acetate/n-hexane=
1/30) to afford pure product 2 as a chartreuse solid (230 mg, 53%).
Compound 5
White solid; yield: 38%; Rf =0.63 (ethyl acetate/n-hexane=1/6);
m.p. 59–608C; 1H NMR (300 MHz, CDCl3): d=8.18–8.08 (m, 2H),
7.58–7.42 (m, 3H), 7.36 (d, J=8.7 Hz, 2H), 6.99 (d, J=8.7 Hz, 2H),
5.34 (s, 2H), 1.32 ppm (s, 9H); 13C NMR (75 MHz, CDCl3): d=175.5
(Cq), 169.0 (Cq), 155.8 (Cq), 145.5 (Cq), 131.8 (CH), 129.3 (CH), 128.0
(CH), 126.9 (CH), 126.8 (Cq), 114.8 (CH), 61.7 (CH2), 34.6 (Cq),
31.9 ppm (CH3); EI-MS: m/z: 308 [M+]; HR-EI-MS: m/z calcd for
C19H20N2O2: 308.1525; found: 308.1532.
1
Rf =0.15 (ethyl acetate/n-hexane=1/12); m.p. 126–1288C; H NMR
(300 MHz, CDCl3): d=8.62 (s, 2H), 8.12–8.00 (m, 4H), 7.95–7.81 (m,
4H), 7.65–7.40 (m, 8H), 7.21 (s, 4H), 6.60 (s, 4H), 6.05 (s, 4H), 4.61
(d, J=13.0 Hz, 4H), 3.82 (t, J=7.5 Hz, 4H), 3.34 (d, J=13.0 Hz, 4H),
2.15–1.90 (m, 4H), 1.38 (s, 18H), 0.95 (s, 18H), 0.84 ppm (t, J=
7.5 Hz, 6H); 13C NMR (75 MHz, CDCl3): d=176.5 (Cq), 167.4 (Cq),
153.1 (Cq), 152.0 (Cq), 146.4 (Cq), 144.4 (Cq), 135.8 (Cq), 131.8 (Cq),
131.0 (Cq), 130.9 (Cq), 130.1 (CH), 128.5 (CH), 126.9 (CH), 125.8
(CH), 125.4 (CH), 124.6 (CH), 77.9 (CH2), 63.8 (CH2), 34.2 (Cq), 33.6
(Cq), 31.9 (CH2), 31.6 (CH3), 31.2 (CH3), 23.3 (CH2), 10.2 ppm (CH3);
HR-FAB-MS: m/z calcd for C84H88N4O6: 1248.6704; found:
1248.6705.
Compound 6
White solid; yield: 69%; Rf =0.36 (ethyl acetate/n-hexane=1/8);
m.p. 63–648C; 1H NMR (300 MHz, CDCl3): d=8.91 (d, J=8.7 Hz,
1H), 8.29 (d, J=7.3 Hz, 1H), 8.02 (d, J=8.3 Hz, 1H), 7.94 (d, J=
8.0 Hz, 1H), 7.70–7.50 (m, 3H), 7.36 (d, J=8.7 Hz, 2H), 7.00 (d, J=
8.7 Hz, 2H), 5.41 (s, 2H), 1.31 ppm (s, 9H); 13C NMR (75 MHz,
CDCl3): d=174.6 (Cq) 169.4 (Cq), 155.9 (Cq), 145.6 (Cq), 134.4 (Cq),
132.6 (CH), 131.1 (Cq), 130.1 (CH), 129.2 (Cq), 128.2 (CH), 127.0
(CH), 126.9 (CH), 126.6 (CH), 125.6 (CH), 123.8 (Cq), 114.9 (CH), 61.8
(CH2), 34.7 (Cq), 32.0 ppm (CH3); EI-MS: m/z: 358 [M+]; HR-EI-MS:
m/z calcd for C23H22N2O2: 358.1681; found: 358.1690.
General Procedures for the Synthesis of Compounds 4–7
A solution of 4-tert-butylphenoxyacetonitrile 3 (1.10 g, 5.80 mmol,
1 equiv) in toluene (25 mL) was added to the respective aryl-N-hy-
droxymoyl chloride derivatives 19--22 (1.5 equiv) and then stirred
at 1108C under argon. Triethylamine (1.5 equiv) was dissolved in
toluene (5 mL) and slowly added with a syringe pump. The reac-
tion mixture was stirred and heated at reflux for 24 h. After the re-
action was complete, the solvent was removed under reduced
pressure. Subsequently, water (100 mL) was added and the suspen-
sion was extracted with CH2Cl2 (100 mL ꢁ 3). The organic layer was
dried over anhydrous MgSO4 and the solvent was removed under
reduced pressure to afford the crude reaction mixture, which was
purified by column chromatography on silica gel (ethyl acetate/n-
hexane=1/30).
Compound 7
Chartreuse solid; yield: 35%; Rf =0.36 (ethyl acetate/n-hexane=1/
10); m.p. 148–1498C; 1H NMR (400 MHz, CDCl3): d=8.61 (d, J=
8.8 Hz, 2H), 7.82 (d, J=8.8 Hz, 2H), 7.67–7.59 (m, 2H), 7.56–7.49
(m, 2H), 7.38 (d, J=8.8 Hz, 2H), 7.05 (d, J=8.8 Hz, 2H), 5.50 (s, 2H),
1.33 ppm (s, 9H); 13C NMR (100 MHz, CDCl3): dc =176.1 (Cq), 167.8
(Cq), 155.8 (Cq), 145.8 (Cq), 133.3 (Cq), 131.7 (Cq), 128.9 (Cq), 127.8
(CH), 127.4 (CH), 127.1 (CH), 126.1 (CH), 125.7 (CH), 120.1 (Cq),
115.1 (CH), 62.0 (CH2), 34.7 (Cq), 32.0 ppm (CH3); EI-MS: m/z: 442
[M+], 444 [M+ +2]; HR-EI-MS: m/z calcd for C27H2335ClN2O2:
442.1448; found: 442.1440.
Compound 9
Compound 4
A solution of compound 8[13] (0.50 g, 0.69 mmol) in toluene (20 mL)
was treated with 19 (0.39 g, 1.51 mmol), and then stirred at 1108C
under argon. Triethylamine (0.21 g, 2.08 mmol) was dissolved in
toluene (8.0 mL) and slowly added with a syringe pump. The reac-
tion was stirred and heated at reflux for 25 h. After the reaction
was complete, the solvent was removed under reduced pressure.
Subsequently, water (100 mL) was added and the suspension was
extracted with CH2Cl2 (3ꢁ100 mL). The organic layer was dried
over anhydrous MgSO4 and the solvent was removed under re-
duced pressure to afford the crude reaction mixture, which was
purified by column chromatography on silica gel (ethyl acetate/n-
hexane=1/15) to afford pure product 9 as a chartreuse solid
(390 mg, 63%). Rf =0.30 (ethyl acetate/n-hexane=1/6); m.p. 158–
1608C; 1H NMR (300 MHz, CDCl3): d=8.65 (s, 1H), 8.12–8.05 (m,
2H), 7.98–7.90 (m, 2H), 7.60–7.38 (m, 4H), 7.15–7.0 (m, 4H), 6.80 (s,
2H), 6.76 (s, 2H), 6.03 (s, 2H), 5.53 (s, 2H), 4.82 (s, 2H), 4.38 (d, J=
13.2 Hz, 2H), 4.30 (d, J=13.5 Hz, 2H), 3.46 (d, J=13.5 Hz, 2H), 3.43
(d, J=13.2 Hz, 2H), 1.33 (s, 18H), 0.94 (s, 9H), 0.91 ppm (s, 9H);
13C NMR (75 MHz, CDCl3): d=174.6 (Cq), 167.6 (Cq), 150.0 (Cq),
149.6 (Cq), 148.8 (Cq), 148.3 (Cq), 148.1 (Cq), 142.3 (Cq), 132.0 (Cq),
Chartreuse solid; yield: 67%; Rf =0.45 (ethyl acetate/n-hexane=1/
12); m.p. 154–1568C; 1H NMR (300 MHz, CDCl3): d=8.64 (s, 1H),
8.12–8.01 (m, 2H), 7.94–7.78 (m, 2H), 7.56–7.42 (m, 4H), 7.39 (d,
J=9.0 Hz, 2H), 7.05 (d, J=9.0 Hz, 2H), 5.51 (s, 2H), 1.33 ppm (s,
9H); 13C NMR (75 MHz, CDCl3): d=175.3 (Cq), 167.5 (Cq), 155.3
(Cq), 145.2 (Cq), 131.0 (Cq), 130.9 (Cq), 130.4 (CH), 128.6 (CH), 127.0
(CH), 126.5 (CH), 125.4 (CH), 125.1 (CH), 119.6 (Cq), 114.5 (CH), 61.4
(CH2), 34.2 (Cq), 31.4 ppm (CH3); FAB-MS: m/z: 409 [M+H+]; HRMS:
m/z calcd for C27H24N2O2: 408.1838; found: 408.1835.
X-ray Single-Crystal Data for 4
C27H24N2O2; M=408.48; triclinic; a=9.0021(3), b=10.6361(4), c=
12.6450(5) ꢂ; a=104.625(3), b=93.677(3), g=109.064(4)8; V=
1092.92(7) ꢂ3; space group P1; Z=2; calculated density
¯
1.241 MgmÀ3
;
crystal dimensions: 0.20ꢁ0.15ꢁ0.10 mm3; T=
295(2) K; l(MoKa)=0.71073 ꢂ; m=0.079 mmÀ1; 20217 reflections
collected; 5019 independent (Rint =0.0215); 280 parameters refined
on F2; R1 =0.0560; wR2[F2]=0.2067 (all data); goodness-of-fit (GOF)
Chem. Asian J. 2015, 00, 0 – 0
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ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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