1
44
H. Nasrallah et al. / Journal of Molecular Catalysis A: Chemical 425 (2016) 136–146
0
8
7
.5H), 8.38 (d, J = 9.2 Hz, 0.5H), 8.24–8.18 (m, 2H), 8.18–8.10 (m, 2H),
.09-7.99 (m, 4H), 7.75–7.69 (m, 2H), 7.50 (tt, J = 7.4, 1.2 Hz, 0.5H),
.42–7.35 (m, 1.5H), 7.33–7.27 (m, 2H), 7.23–7.13 (m, 1H), 7.10
evaporated under reduced pressure. The crude product was
purified by flash chromatography on silica gel (CH Cl ) giving L as
2
2
◦
1
a tan powder (92/8 E/Z mixture, 751.1 mg, 81%). Mp = 107 C. H
(
0
(
td, J = 6.8, 1.4 Hz, 1H), 7.07–7.02 (m, 1.5H), 6.97 (dd, J = 6.8, 1.5 Hz,
.5H), 6.73 (s, 1H), 6.44 (br.s, 0.5H), 6.12 (d, J = 2.8 Hz, 0.5H), 6.01
br.s, 0.5H), 5.69 (d, J = 2.9 Hz, 0.5H), 5.27 (s, 2H), 4.10 (t, J = 6.2 Hz,
H), 4.02–3.93 (m, 2H), 3.88–3.69 (m, 4.5H), 3.67–3.59 (m, 0.5H),
.73–2.66 (3 s, 6H), 2.35 (s, 1.5H), 2.24 (s, 1.5H), 2.22–2.11 (m,
.5H), 2.09 (s, 1.5H), 2.07–2.01 (m, 2.5H), 1.86 (s, 1.5H), 1.67–1.36
NMR (400 MHz, CDCl , E isomer) ␦ = 8.31 (d, J = 9.2 Hz, 1H), 8.16 (d,
3
J = 7.6 Hz, 2H), 8.11 (d, J = 7.7 Hz, 1H), 8.09 (d, J = 9.1 Hz, 1H), 8.03 (s,
2H), 7.99 (dd, J = 8.0, 7.2 Hz, 1H), 7.87 (d, J = 7.8 Hz, 1H), 7.37–7.29
(m, 2H), 6.98 (br.s, 1H), 6.83 (d, J = 8.6 Hz, 1H), 6.50 (br.dq, J = 11.6,
1.9 Hz, 1H), 5.80 (dq, J = 11.6, 7.1 Hz, 1H), 4.43 (sept, J = 6.0 Hz, 1H),
3.45 (t, J = 7.3 Hz, 2H), 2.43–2.36 (m, 2H), 2.36–2.25 (m, 2H), 1.84
1
2
5
m, 15H), 1.17–0.87 (m, 15H). 13C NMR (101 MHz, CDCl ) (2 con-
(dd, J = 7.1, 1.9 Hz, 3H), 1.31 (d, J = 6.0 Hz, 6H). C NMR (101 MHz,
13
(
3
formers) ␦ = 292.6 (d, JP-C = 5.5 Hz), 292.5 (d, JP-C = 5.8 Hz), 217.6 (d,
JP-C = 74 Hz), 217.3 (d, JP-C = 73 Hz), 158.7, 157.4, 145.2, 144.9, 141.0,
CDCl ) ␦ = 170.9, 152.5, 135.8, 131.5, 131.0, 130.5, 130.0, 128.9,
128.3, 127.6, 127.5, 127.4, 127.0, 126.8, 125.9, 125.2, 125.2, 125.1,
125.0, 124.9, 123.4, 122.6, 120.0, 115.0, 71.5, 36.8, 32.7, 27.3,
3
141.0, 141.0, 140.9, 139.4, 139.1, 138.6, 138.5, 138.5, 138.0, 137.9,
137.1, 137.0, 137.0, 137.0, 136.9, 136.9, 136.6, 135.6, 132.6, 131.7,
131.7, 131.4, 131.4, 131.4, 131.0, 130.9, 130.9, 130.0, 129.5, 129.5,
129.3, 129.2, 129.1, 129.0, 128.9, 128.7, 128.2, 128.2, 127.9, 127.8,
127.6, 127.5, 127.5, 127.5, 127.2, 127.1, 127.0, 127.0, 126.6, 126.4,
126.1, 126.1, 125.4, 125.4, 125.3, 125.3, 125.1, 124.9, 124.6, 124.6,
123.6, 123.6, 116.2, 116.0, 114.6, 114.5, 114.4, 112.0, 71.9, 71.9, 67.3,
67.2, 64.8, 64.2, 53.6, 52.8 (d, JP-C = 3.3 Hz), 52.7(d, JP-C = 2.9 Hz), 52.3
22.3, 14.9. HR-MS (ESI): m/z = 484.2245, calcd. for C32H31NO Na
2
+
[M + Na] : 484.2247 (0 ppm).
C1: In
a
Schlenk tube were placed under argon
7
(73.4 mg,
0.06 mmol), 2,2,2-trifluoro-N-(4-isopropoxy-3-
vinylphenyl)acetamide (16.4 mg, 0.06 mmol) and CuCl (6.5 mg,
0.07 mmol), then CH Cl (1.8 mL) was added and the solution
2
2
◦
was heated at 35 C for 16 h under stirring. The mixture was con-
centrated under reduced pressure then dissolved in acetone and
filtered on celite bed. The crude was purified by flash chromatog-
raphy on silica gel (pentane/AcOEt, 7:3 to 1:1). The solid obtained
was precipitated from CH Cl by the addition of pentane, giving C1
(
d, JP-C = 1.7 Hz), 52.2 (d, JP-C = 1.6 Hz), 35.7, 33.0 (d, JP-C = 16.6 Hz),
32.9 (d, JP-C = 16.3 Hz), 30.5, 30.1, 30.1, 29.5, 29.5, 29.4, 28.8, 28.0,
28.0, 27.9, 27.9, 27.8, 27.8, 27.7, 26.4, 25.6, 24.3, 21.3, 21.2, 20.9,
2
0.8, 20.4, 20.3, 19.3, 19.0, 18.9, 18.8. 31P NMR (162 MHz, CDCl3)
2
2
1
◦
(
2 conformers) ␦ = 26.69, 25.85. HR-MS (MALDI): m/z = 1187.4900,
as a light green powder (54.2 mg, 90%). H NMR (400 MHz, 55 C,
+
•
calcd. for C73H84ClN O PRu [M−Cl] : 1187.4924 (2 ppm).
CDCl ) ␦ = 16.41 (s, 1H), 8.28 (d, J = 9.2 Hz, 1H), 8.17 (d, J = 7.6 Hz,
2
2
3
N-(4-isopropoxy-3-vinylphenyl)-4-(pyren-1-yl)butanamide
1H), 8.13 (d, J = 7.5 Hz, 1H), 8.06 (d, J = 7.8 Hz, 1H), 8.02–7.90 (m,
6H), 7.33 (br.d, J = 8.7 Hz, 1H), 7.08 (s, 2H), 7.02 (br.s, 1H), 6.77 (s,
2H), 6.43 (br.d, J = 8.8 Hz, 1H), 5.26 (s, 2H), 4.68 (sept, J = 6.1 Hz, 1H),
4.23–4.13 (m, 6H), 3.94 (br.t, J = 6.0 Hz, 2H), 2.51 (s, 6H), 2.43 and
2.42 (2 s, 9H), 2.21 (tt, J ∼ 6.0, ∼ 6.0 Hz, 2H), 1.21 (d, J = 6.1 Hz, 6H).
(
8): In a dry round bottomed flask, 4-isopropoxy-3-vinylaniline
hydrochloride [22] (500 mg, 2.34 mmol) was dissolved in CH Cl
2
2
(
25 mL) and deprotonated with pyridine (208 L, 2.57 mmol). After
3
0 min under stirring, the organic phase was washed successively
13
◦
C NMR (101 MHz, CDCl , 55 C; partial: due to low solubility,
3
with deionized water and brine, dried over MgSO and filtered. The
4
resulting solution was completed to 40 mL with CH Cl2 then 4-
uncomplete set of signals was obtained) ␦ = 293.3, 201.5, 159.3,
149.8, 139.0, 131.4, 131.2, 130.8, 129.8, 129.8, 129.7, 129.4, 129.4,
127.9, 127.4, 127.3, 127.2, 125.8, 125.5, 125.0, 124.9, 124.7, 124.5,
123.1, 120.8, 114.9, 114.5, 112.6, 75.6, 71.7, 67.1, 65.4, 51.7, 51.5,
2
(
pyren-1-yl)butanoic acid (674.6 mg, 2.34 mmol), DCC (482.7 mg,
2
.34 mmol) and DMAP (571.7 mg, 4.68 mmol) were successively
◦
added at 0 C. The mixture was stirred for 16 h at rt then treated
with HCl (1 M, 40 mL) and extracted with CH Cl . The organic phase
29.5, 21.2, 20.9, 19.5 (br.m). 19F NMR (376 MHz, CDCl ) ␦ = −75.5.
2
2
3
was washed with brine, dried over MgSO , filtered and evaporated
HR-MS (ESI): m/z = 1010.2230, calcd. for
[M-H] : 1010.2252 (2 ppm). Anal. Calcd for C52H52Cl F N O Ru:
C
H
Cl F N O Ru
4
52 51
2
3
3
4
−
under reduced pressure. The crude product was purified by flash
2
3
3
4
chromatography on silica gel (CH Cl ) giving 8 as a white powder
C, 61.72; H, 5.18; N, 4.15. Found: C, 61.93; H, 5.27; N, 4.23.
C2: Schenk tube was charged
2
2
◦
1
(
(
(
772.1 mg, 74%). Mp = 162 C. H NMR (400 MHz, CDCl ) ␦ = 8.29
d, J = 9.2 Hz, 1H), 8.18–8.14 (m, 2H), 8.10 (d, J = 7.7 Hz, 1H), 8.08
d, J = 9.2 Hz, 1H), 8.02 (s, 2H), 7.99 (dd, J = 7.9, 7.4 Hz, 1H), 7.86 (d,
A
with
3
(SIPr)RuCl (PPh )(Indenylidene) (101.5 mg, 0.10 mmol) and
2 3
compound 8 (44.8 mg, 0.10 mmol). The powders were placed
J = 7.8 Hz, 1H), 7.49 (d, J = 2.7 Hz, 1H), 7.36 (dd, J = 8.8, 2.7 Hz, 1H),
under argon, dissolved in dry and degazed CH Cl (2.7 mL) and
heated in an oil bath at 40 C for 24 h. The heterogeneous mixture
was then concentrated by half under reduced pressure, then
2
2
◦
7.05 (br.s, 1H), 7.01 (dd, J = 17.8, 11.2 Hz, 1H), 6.80 (d, J = 8.8 Hz,
1H), 5.70 (dd, J = 17.8, 1.5 Hz, 1H), 5.24 (dd, J = 11.1, 1.4 Hz, 1H),
4.45 (sept, J = 6.0 Hz, 1H), 3.42 (t, J = 7.3 Hz, 2H), 2.40–2.34 (m,
2
H), 2.33–2.24 (m, 2H), 1.32 (d, J = 6.1 Hz, 6H). 13C NMR (101 MHz,
distilled Et O (15 mL) was added whereupon a green powder
2
precipitates. The filtrate was taken out by the means of a filtering
CDCl ) ␦ = 170.9, 152.1, 135.8, 131.6, 131.5, 131.1, 131.0, 130.1,
cannula and the solid washed with Et O until the liquid became
3
2
1
1
28.9, 128.5, 127.6, 127.6, 127.5, 126.9, 126.0, 125.2, 125.1, 125.1,
colorless. The solid was dried under vacuum to afford C2 as a light
24.9, 123.5, 121.1, 118.6, 115.3, 114.7, 71.6, 36.8, 32.7, 27.3, 22.3.
green powder (59.4 mg, 60%). 1H NMR (400 MHz, CD Cl ) ␦ = 16.27
2
2
+
HR-MS (ESI): m/z = 470.2090, calcd. for C31H29NO Na [M+Na] :
4
(s, 1H), 8.37 (d, J = 9.2 Hz, 1H), 8.24–8.12 (m, 4H), 8.10–8.05 (m, 2H),
8.02 (t, J = 7.6 Hz, 1H), 7.92 (d, J = 7.8 Hz, 1H), 7.78 (dd, J = 8.8, 2.6 Hz,
1H), 7.53 (t, J = 7.7 Hz, 2H), 7.38 (d, J = 7.8 Hz, 4H), 7.09 (s, 1H), 6.83
(d, J = 2.6 Hz, 1H), 6.75 (d, J = 8.9 Hz, 1H), 4.85 (sept, J = 6.0 Hz, 1H),
4.17 (s, 4H), 3.57 (sept, J = 6.6 Hz, 4H), 3.45 (t, J = 7.6 Hz, 2H), 2.43
(t, J = 7.3 Hz, 2H), 2.27 (tt, J ∼ 7.5, ∼ 7.5 Hz, 2H), 1.31 (d, J = 6.1 Hz,
6H), 1.28–1.17 (m, 24H). 13C NMR (101 MHz, CD Cl ) ␦ = 213.2,
2
70.2091 (0 ppm).
N-(4-isopropoxy-3-(prop-1-en-1-yl)phenyl)-4-(pyren-
1
-yl)butanamide (L): In
a
dry round bottomed flask
4
-isopropoxy-3-(prop-1-en-1-yl)aniline hydrochloride[8b] (92/8
E/Z mixture, 455.3 mg, 2.0 mmol) was dissolved in CH Cl (25 mL)
2
2
and deprotonated with pyridine (177 L, 2.2 mmol). After 30 min
under stirring the organic phase was washed successively with
deionized water and brine, dried over MgSO4 and filtered. The
2
2
171.1, 149.8, 149.2, 144.4, 137.3, 136.7, 133.5, 132.0, 131.5, 130.5,
130.2, 129.4, 128.0, 128.0, 127.9, 127.2, 126.5, 125.6, 125.4, 125.4,
125.3, 124.8, 124.0, 121.4, 113.6, 113.4, 75.8, 55.2, 37.2, 33.2,
29.3, 27.7, 26.9, 23.7, 22.0. HR-MS (ESI): m/z = 995.3502, calcd.
resulting solution was completed to 40 mL with CH Cl2 then
2
4
2
-(pyren-1-yl)butanoic acid (576.7 mg, 2.0 mmol), DCC (412.7 mg,
+
•
for C57H65N O Cl Ru [M] : 995.34918 (1 ppm). Anal. Calcd for
3 2 2
.0 mmol) and DMAP (488.7 mg, 4.00 mmol) were successively
◦
added at 0 C. The mixture was stirred for 16 h at rt then treated
with HCl (1 M, 40 mL) and extracted with CH Cl . The organic
C57H65N O Cl Ru: C, 68.73; H, 6.58; N, 4.22. Found: C, 68.35; H,
3 2 2
6.67; N, 3.99.
2
2
phase was washed with brine, dried over MgSO , filtered and
4