One-Pot Wittig Reaction Cascades
133.2, 128.73, 128.65, 128.6, 128.2, 126.3, 40.6, 30.3 ppm; HRMS (EI, m/
z): calcd for C15H14O 210.1045, found 210.1034.
2-(4-Bromobenzyl)-3-(4-bromophenyl)-3-hydroxy-1-phenylpropan-1-one
(12c)
5-Methyl-1-phenylhexan-1-one (11d)
syn/anti=41:59; 1H NMR (400 MHz, CDCl3): d=7.65 (d, J=7.4 Hz,
1.18H), 7.53 (d, J=7.3 Hz, 0.82H), 7.49–7.11 (m, 9H), 6.94 (d, J=8.3 Hz,
1.18H), 6.81 (d, J=8.3 Hz, 0.82H), 4.99 (d, J=4.8 Hz, 0.41H), 4.84 (m,
0.59H), 4.09–3.85 (m, 1H), 3.76 (d, J=5.0 Hz, 1.18H), 3.50 (s, 0.82H),
3.12 (dd, J=13.6, 10.4 Hz, 0.41H), 3.03–2.87 (m, 1H), 2.76 ppm (dd, J=
13.5, 6.3 Hz, 0.59H); 13C NMR (100 MHz, CDCl3): d=204.9, 203.9,
141.5, 140.7, 138.0, 137.6, 137.3, 137.0, 133.5, 133.5, 131.6, 131.6, 131.5,
131.4, 130.8, 130.8, 128.6, 128.6, 128.2, 128.2, 128.0, 128.0, 121.7, 121.6,
120.5, 120.1, 74.7, 73.3, 55.2, 54.3, 35.8, 33.0 ppm; HRMS (EI, m/z): calcd
for C15H13BrO (M-C7H5BrO) 288.0150, found 288.0146
1H NMR (400 MHz, CDCl3): d=7.95–7.97 (m, 2H), 7.53–7.55 (m, 1H),
7.44–7.48 (m, 2H), 2.95 (t, 2H, J=7.4 Hz), 1.72–1.76 (m, 2H), 1.58–1.61
(m, 1H), 1.24–1.29 (m, 2H), 0.86–0.91 ppm (m, 6H); 13C NMR
(100 MHz, CDCl3): d=200.8, 137.2, 133.0, 128.7, 128.2, 39.0, 38.8, 28.1,
22.7, 22.4 ppm; HRMS (EI, m/z): calcd for C13H18O 190.1358, found
190.1343.
4-(4-Nitrophenyl)butan-2-one (11e)
1H NMR (400 MHz, CDCl3): d=8.14 (d, 2H, J=8.6 Hz), 7.35 (d, 2H, J=
8.5 Hz), 3.00 (t, 2H, J=7.3 Hz), 2.82 (t, 2H, J=7.3 Hz), 2.17 ppm (s,
3H); 13C NMR (100 MHz, CDCl3): d=206.8, 149.1, 146.7, 129.4, 123.9,
44.3, 30.2, 29.5 ppm; HRMS (EI, m/z): calcd for C10H11NO3 193.0739,
found 193.0734.
2-Benzyl-3-hydroxy-1-(4-methoxyphenyl)-3-phenylpropan-1-one (12d)
syn/anti=23:77; 1H NMR (300 MHz, CDCl3): d=7.64 (d, J=8.9 Hz,
1.54H), 7.58–7.51 (m, 0.46H), 7.43 (d, J=7.1 Hz, 0.46H), 7.37–6.99 (m,
9.08H), 6.96–6.88 (m, 0.46H), 6.80–6.66 (m, 2H), 5.09 (d, J=4.0 Hz,
0.23H), 4.93 (apparent d, J=5.4 Hz, 0.77H), 4.04–4.01 (m, 1H), 3.84–
3.75 (m, 1.77H), 3.63 (s, 0.23H), 3.15 (dd, J=13.6, 10.5 Hz, 0.23H), 3.08–
2.94 (m, 1H), 2.93 ppm (dd, J=13.4, 6.5 Hz, 0.77H); 13C NMR
(100 MHz, CDCl3): d=203.8, 203.4, 163.7, 143.0, 141.9, 139.7, 139.0,
130.9, 130.8, 130.7, 130.3, 129.2, 129.1, 128.6, 128.5, 128.5, 128.4, 127.7,
127.7, 126.5, 126.3, 126.2, 113.9, 113.7, 113.7, 75.4, 74.1, 55.5 (2C), 54.2,
36.9, 33.4 ppm; HRMS (EI, m/z): calcd for C16H16O2 (M-C7H6O)
240.1150, found 240.1144.
4-(4-Bromophenyl)butan-2-one (11 f)
1H NMR (400 MHz, CDCl3): d=7.38–7.40 (m, 2H), 7.05–7.07 (m, 2H),
2.84 (t, 2H, J=7.2 Hz), 2.73 (t, 2H, J=7.2 Hz), 2.13 ppm (s, 3H);
13C NMR (100 MHz, CDCl3): d=207.6, 140.1, 131.6, 130.2, 120.0, 44.9,
30.2, 29.1 ppm; HRMS (EI, m/z): calcd for C10H11BrO 225.9993, found
225.9993.
1-(4-Bromophenyl)-3-(4-nitrophenyl)propan-1-one (11g)
1H NMR (400 MHz, CDCl3): d=8.15 (d, 2H, J=8.6 Hz), 7.81 (d, 2H, J=
8.6 Hz), 7.61 (d, 2H, J=8.6 Hz), 7.42 (d, 2H, J=8.6 Hz), 3.32 (t, 2H, J=
7.3 Hz), 3.17 ppm (t, 2H, J=7.2 Hz); 13C NMR (100 MHz, CDCl3): d=
197.2, 149.0, 146.7, 135.3, 132.2, 129.6, 129.5, 128.7, 123.9, 39.5, 29.7 ppm;
HRMS (EI, m/z): calcd for C15H12BrNO3 333.0001, found 332.9996.
2-(HydroxyACTHNUTRGNEUG(N phenyl)methyl)-1,5-diphenylpentan-1-one (12e)
syn/anti=33:67. 1H NMR (400 MHz, CDCl3): d=7.87–7.85 (m, 2H),
7.53–7.51 (m, 1H), 7.42–7.40 (m, 2H), 7.36–7.07 (m, 8H), 6.97 (apparent
d, J=7.3 Hz, 2H), 5.03 (d, J=4.7 Hz, 0.33H), 4.96 (d, J=7.0 Hz, 0.67H),
3.84–3.79 (m, 1H), 3.18–3.17 (m, 1H), 2.48–2.42 (m, 2H), 2.02–1.90 (m,
0.33H), 1.85–1.70 (m, 1H), 1.55–1.42 ppm (m, 2.67H); 13C NMR
(100 MHz, CDCl3): d=205.7, 205.1, 142.8, 142.0, 141.8, 138.2, 137.3,
133.5, 133.4, 128.8, 128.7, 128.6, 128.5, 128.4, 128.4, 128.3, 127.9, 127.6,
126.5, 126.3, 125.9, 125.8, 76.2, 74.1, 52.9, 52.8, 36.2, 36.0, 30.4, 29.7, 29.1,
27.3 ppm; HRMS (EI, m/z): calcd for C17H18O (M-C7H6O) 238.1352,
found 238.1351.
1,3-Bis(4-bromophenyl)propan-1-one (11h)
1H NMR (400 MHz, CDCl3): d=7.79–7.81 (m, 2H), 7.58–7.60 (m, 2H),
7.39–7.41 (m, 2H), 7.11 (d, 2H, J=8.3 Hz), 3.23 (t, 2H, J=7.5 Hz),
3.01 ppm (t, 2H, J=7.5 Hz); 13C NMR (100 MHz, CDCl3): d=197.9,
140.1, 135.5, 132.1, 131.7, 130.3, 129.6, 128.5, 120.1, 40.1, 29.4 ppm;
HRMS (EI, m/z): calcd for C15H12Br2O 365.9255, found 365.9253.
3-(HydroxyACTHNUGRTNEUNG(phenyl)methyl)-6-phenylhexan-2-one (12 f)
3-(4-Bromobenzyl)-4-(4-bromophenyl)-4-hydroxybutan-2-one (12a)
syn/anti=32:68. Less polar syn isomer: 1H NMR (300 MHz, CDCl3): d=
7.38–7.22 (m, 7H), 7.18–7.15 (m, 1H), 7.11–7.08 (m, 2H), 4.88 (dd, J=
5.7, 1.6 Hz, 1H), 2.93–2.87 (m, 1H), 2.64 (d, J=2.4 Hz, 1H), 2.54 (t, J=
7.7 Hz, 2H), 1.96 (s, 3H), 1.84–1.65 (m, 2H), 1.64–1.45 ppm (m, 2H);
13C NMR (100 MHz, CDCl3): d=212.8, 141.9, 141.9, 128.5, 128.3, 127.8,
126.2, 125.8, 77.2, 74.0, 59.5, 36.1, 31.7, 29.7, 26.9 ppm. More polar anti
isomer: 1H NMR (300 MHz, CDCl3): d=7.35–7.08 (m, 8H), 7.08–7.05
(m, 2H), 4.76 (apparent d, J=7.7 Hz, 1H), 2.97–2.89 (m, 1H), 2.53–2.47
(m, 2H), 2.10 (s, 3H), 1.70–1.37 ppm (m, 4H); 13C NMR (100 MHz,
CDCl3): d=213.7, 142.5, 141.8, 128.7, 128.5, 128.4, 128.1, 126.4, 126.0,
75.8, 59.1, 35.9, 32.1, 29.1, 29.1 ppm. HRMS EI (m/z): calcd for C12H16O
(M-C7H6O) 176.1201, found 176.1195.
syn/anti=30:70. Less polar syn isomer: 1H NMR (300 MHz, CDCl3): d=
7.49 (d, J=8.4 Hz, 2H), 7.35 (d, J=8.3 Hz, 2H), 7.35 (d, J=8.3 Hz, 2H),
6.92 (d, J=8.4 Hz, 2H), 4.91 (d, J=5.46 Hz, 1H), 3.16–3.06 (m, 1H), 3.01
(brs, 1H), 2.88 (d, J=7.4 Hz, 1H), 1.68 ppm (s, 3H); 13C NMR
(100 MHz, CDCl3): d=212.6, 140.6, 138.2, 131.8, 131.7, 130.7, 128.0,
121.9, 120.4, 73.2, 61.2, 33.0 ppm (2C). More polar anti isomer: 1H NMR
(400 MHz, CDCl3): d=7.48 (d, J=8.4 Hz, 2H), 7.37 (d, J=8.3 Hz, 2H),
7.19 (d, J=8.4 Hz, 2H), 6.95 (d, J=8.3 Hz, 2H), 4.72 (apparent t, 1H,
J=5.6 Hz), 3.10–3.18 (m, 2H), 2.86 (dd, 1H, J=13.4, 10.0 Hz), 2.55 (dd,
1H, J=13.4, 5.5 Hz), 1.84 ppm (s, 3H); 13C NMR (100 MHz, CDCl3): d=
213.4, 141.3, 137.3, 131.9, 131.8, 130.6, 127.9, 122.0, 120.6, 74.9, 60.3, 35.3,
33.6 ppm; HRMS (EI, m/z): calcd for C10H11BrO (M-C7H5BrO) 225.9993,
found 255.9989.
2-Benzyl-3-(4-chlorophenyl)-3-hydroxy-1-phenylpropan-1-one (12g)
syn/anti=37:63; 1H NMR (400 MHz, CDCl3): d=7.65 (d, J=7.3 Hz,
1.26H), 7.55–7.48 (m, 0.74H), 7.48–7.37 (m, 1H), 7.35–6.99 (m, 10.26H),
6.93 (d, J=6.8 Hz, 0.74H), 5.08 (d, J=4.3 Hz, 0.37H), 4.92 (t, J=5.6 Hz,
0.63H), 4.08–3.98 (m, 1H), 3.70 (d, J=7.1 Hz, 0.63H), 3.44 (s, 0.37H),
3.14 (dd, J=13.5, 10.4 Hz, 0.37H), 3.08–2.97 (m, 1H), 2.93 ppm (dd, J=
13.5, 7.0 Hz, 0.63H); 13C NMR (100 MHz, CDCl3): d=205.5, 204.8,
141.4, 140.3, 139.1, 138.4, 137.7, 137.3, 133.4, 133.4, 133.3, 129.1, 129.1,
128.7, 128.6, 128.6, 128.6, 128.5, 128.4, 128.3, 128.2, 127.8, 127.6, 126.7,
126.3, 74.6, 73.4, 55.5, 54.6, 36.7, 33.7 ppm (2C); HRMS (EI, m/z): calcd
for C15H14O (M-C7H5ClO) 210.1039, found 210.1037.
2-Benzyl-1,3-diphenyl-3-hydroxypropan-1-one (12b)
syn/anti=34:66; 1H NMR (400 MHz, CDCl3): d=7.63 (d, J=7.5 Hz,
1.32H), 7.53 (d, J=7.6 Hz, 0.68H), 7.42–6.99 (m, 12.32H), 6.96 (d, J=
6.9 Hz, 0.68H), 5.08 (d, J=4.6 Hz, 0.34H), 4.95 (d, J=6.0 Hz, 0.66H),
4.09–4.06 (m, 1H), 3.18 (dd, J=13.5, 10.6 Hz, 0.34H), 3.08–3.00 (m, 1H),
2.85 ppm (dd, J=13.5, 6.3 Hz, 0.66H); 13C NMR (100 MHz, CDCl3): d=
205.7, 204.9, 142.7, 141.7, 139.4, 138.7, 138.1, 137.4, 133.1, 133.1, 129.1,
128.6, 128.6, 128.5, 128.4, 128.4, 128.3, 128.2, 127.8, 127.7, 126.5, 126.3,
126.3, 126.2, 75.4, 74.1, 55.7, 54.8, 36.7, 33.6 ppm; HRMS (EI, m/z): calcd
for C15H14O (M-C7H6O) 210.1039, found 210.1042.
2-Benzyl-3-(furan-2-yl)-3-hydroxy-1-phenylpropan-1-one (12h)
1
syn/anti=50:50; H NMR (300 MHz, CDCl3): d=7.92–7.71 (m, 1H), 7.61
(d, J=7.2 Hz, 1H), 7.48–7.40 (m, 0.5H), 7.35–7.03 (m, 8H), 6.27–6.24 (m,
Chem. Asian J. 2012, 7, 351 – 359
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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