2754
X. Liu et al.
PAPER
13C NMR (100 MHz, CDCl3): d = 201.48, 137.83, 133.26, 129.08,
128.72, 127.77, 119.61, 75.79, 46.10, 26.32.
HRMS (EI+): m/z calcd for C13H1535ClO2 [M+ – H2O]: 238.0761;
found: 238.0762.
HRMS (EI+): m/z calcd for C12H1379BrO [M+]: 252.0150; found:
252.0138; m/z calcd for C12H1381BrO [M+]: 254.0129; found:
254.0159.
4-(Dimethoxymethyl)dec-1-en-4-ol (4f)
IR (KBr): 3587, 3502, 3078, 2954, 2931, 2862, 1643, 1465, 1080,
979, 918 cm–1.
a-Hydroxy-a-allyl Aldehyde Acetals 4; General Procedure
Allyl bromide (1.2 mmol) and Sm (1.1 mmol) were mixed in anhyd
THF (10 mL) under N2 at r.t. The mixture was stirred for about 10
min, and a purple color was formed. The stirring was continued un-
til the Sm powder had disappeared (1 h). Then a solution of the sub-
strate a,a-dihalo ketone was added dropwise (the reaction was
monitored by TLC). The reaction mixture was stirred for 10 min and
then MeOH (or EtOH) (10 mL) was added followed by NaOMe (or
NaOEt) (5 mmol) in portions. The mixture was stirred for 4 h and
filtered. The solvent was removed by evaporation under reduced
pressure to give the crude product as an oil, which was purified by
column chromatography on silica gel (eluent: PE–EtOAc, 15:1).
1H NMR (400 MHz, CDCl3): d = 5.94–5.84 (m, 1 H), 5.11–5.06 (m,
2 H), 4.12 (s, 1 H), 3.54 (d, J = 1.2 Hz, 6 H), 2.32–2.29 (m, 2 H),
2.05 (s, 1 H), 1.52–1.48 (m, 2 H), 1.38–1.28 (m, 8 H), 0.88 (t,
J = 6.8 Hz, 3 H).
13C NMR (100 MHz, CDCl3): d = 134.59, 118.23, 110.04, 76.31,
58.61 (d, J = 4.2 Hz), 39.90, 35.21, 32.26, 30.43, 23.23, 23.08,
14.54.
HRMS (EI+): m/z calcd for C13H24O2 [M+ – H2O]: 212.1776; found:
212.1779.
2-(4-Bromophenyl)-1,1-dimethoxypent-4-en-2-ol (4m)
IR (KBr): 3558, 3078, 2937, 2839, 1643, 1604, 1496, 1450, 1188,
1072, 979, 918, 833 cm–1.
1,1-Dimethoxy-2-phenylpent-4-en-2-ol (4a)
IR (KBr): 3556, 3070, 2939, 2839, 1643, 1604, 1496, 1450, 1188,
1149, 1072, 979, 918, 763, 702 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.47–7.38 (m, 4 H), 5.65–5.54 (m,
1 H), 5.10–5.02 (m, 2 H), 4.21 (s, 1 H), 3.43 (d, J = 19.2 Hz, 6 H),
2.77–2.61 (m, 3 H).
1H NMR (400 MHz, CDCl3): d = 7.52–7.21 (m, 5 H), 5.68–5.57 (m,
1 H), 5.08–4.98 (m, 2 H), 4.24 (s, 1 H), 3.38 (d, J = 14.8 Hz, 6 H),
2.81–2.65 (m, 3 H).
13C NMR (100 MHz, CDCl3): d = 141.54, 133.33, 131.31, 128.81,
121.53, 119.31, 110.61, 77.87, 58.60 (d, J = 13.8 Hz), 41.21.
13C NMR (100 MHz, CDCl3): d = 142.57, 133.90, 128.29, 127.37,
126.88, 118.90, 110.85, 78.11, 58.41 (d, J = 10.1 Hz), 41.30.
HRMS (EI+): m/z calcd for C13H1579BrO2 [M+ – H2O]: 282.0255;
found: 282.0245; m/z calcd for C13H1581BrO2 [M+ – H2O]:
284.0235; found: 284.0235.
HRMS (EI+): m/z calcd for C13H16O2 [M+ – H2O]: 204.1150; found:
204.1156.
1,1-Dimethoxy-2-(4-methoxyphenyl)pent-4-en-2-ol (4n)
IR (KBr): 3556, 3078, 2954, 2839, 1612, 1512, 1465, 1249, 1180,
1080, 979, 918, 833 cm–1.
1,1- Dimethoxy-2-p-tolylpent-4-en-2-ol (4b)
IR (KBr): 3564, 3078, 2931, 2839, 1643, 1512, 1450, 1188, 1149,
1080, 979, 918, 817 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.44–6.86 (m, 4 H), 5.69–5.58 (m,
1 H), 5.10–5.01 (m, 2 H), 4.21 (s, 1 H), 3.80 (s, 3 H), 3.41 (d,
J = 22.4 Hz, 6 H), 2.81–2.61 (m, 3 H).
1H NMR (400 MHz, CDCl3): d = 7.40–7.13 (m, 4 H), 5.68–5.57 (m,
1 H), 5.10–5.00 (m, 2 H), 4.23 (s, 1 H), 3.41 (d, J = 14.8 Hz, 6 H),
2.81–2.62 (m, 3 H), 2.33 (s, 3 H).
13C NMR (100 MHz, CDCl3): d = 158.83, 134.49, 133.91, 128.02,
118.86, 113.57, 111.04, 77.82, 58.48 (d, J = 23.5 Hz), 55.54, 41.06.
13C NMR (100 MHz, CDCl3): d = 139.51, 136.83, 133.96, 129.02,
126.74, 118.83, 110.94, 77.96, 58.42 (d, J = 15.5 Hz), 41.25, 21.47.
HRMS (EI+): m/z calcd for C14H18O3 [M+ – H2O]: 234.1256; found:
234.1262.
HRMS (EI+): m/z calcd for C14H20O3 [M+]: 236.1412; found:
236.1414.
1,1-Dimethoxy-2-(naphthalen-2-yl)pent-4-en-2-ol (4o)
IR (KBr): 3564, 3062, 2939, 2831, 1643, 1543, 1450, 1072, 972,
910, 748, 694 cm–1.
2-(4-Fluorophenyl)-1,1-dimethoxypent-4-en-2-ol (4c)
IR (KBr): 3564, 3078, 2939, 2839, 1643, 1604, 1512, 1450, 1226,
1188, 1072, 979, 918, 840 cm–1.
1H NMR (400 MHz, CDCl3): d = 8.03–7.42 (m, 7 H), 5.65–5.59 (m,
1 H), 5.12–4.98 (m, 2 H), 4.33 (s, 1 H), 3.39 (d, J = 13.6 Hz, 6 H),
2.94–2.74 (m, 3 H).
1H NMR (400 MHz, CDCl3): d = 7.51–6.99 (m, 4 H), 5.66–5.56 (m,
1 H), 5.10–5.02 (m, 2 H), 4.21 (s, 1 H), 3.43 (d, J = 22.8 Hz, 6 H),
2.79–2.63 (m, 3 H).
13C NMR (100 MHz, CDCl3): d = 140.13, 133.78, 133.59, 132.94,
128.82, 127.91, 127.83, 126.31, 126.27, 125.91, 125.20, 119.11,
110.89, 78.34, 58.49 (d, J = 11.1 Hz), 41.29.
13C NMR (100 MHz, CDCl3): d = 162.28 (1JC,F = 243.7 Hz), 138.13
(4JC,F = 3.1 Hz), 133.52, 128.64 (3JC,F = 7.9 Hz), 119.16, 115.00
(2JC,F = 20.9 Hz), 110.86, 77.82, 58.56 (d, J = 18.1 Hz), 41.25.
HRMS (EI+): m/z calcd for C17H18O2 [M+ – H2O]: 254.1307; found:
254.1309.
HRMS (EI+): m/z calcd for C13H15FO2 [M+ – H2O]: 222.1056;
found: 222.1060.
1,1-Diethoxy-2-phenylpent-4-en-2-ol (4p)
IR (KBr): 3587, 3078, 2939, 2839, 1643, 1597, 1496, 1450, 1188,
1149, 1080, 979, 918, 752, 694 cm–1.
2-(4-Chlorophenyl)-1,1-dimethoxypent-4-en-2-ol (4d)
IR (KBr): 3556, 3078, 2939, 2839, 1643, 1597, 1496, 1450, 1188,
1080, 979, 918, 833 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.53–7.22 (m, 5 H), 5.70–5.59 (m,
1 H), 5.10–4.99 (m, 2 H), 4.36 (s, 1 H), 3.79–3.67 (m, 2 H), 3.46–
3.29 (m, 2 H), 2.87–2.68 (m, 3 H), 1.15 (t, J = 6.8 Hz, 6 H).
1H NMR (400 MHz, CDCl3): d = 7.46–7.27 (m, 4 H), 5.63–5.57 (m,
1 H), 5.07–4.99 (m, 2 H), 4.20 (s, 1 H), 3.40 (d, J = 19.6 Hz, 6 H),
2.79–2.65 (m, 3 H).
13C NMR (100 MHz, CDCl3): d = 142.55, 134.12, 128.20, 127.29,
127.01, 118.65, 108.38, 77.93, 66.39 (d, J = 5.0 Hz), 40.80, 15.73
(d, J = 12.3 Hz).
13C NMR (100 MHz, CDCl3): d = 141.02, 133.38, 133.29, 128.45,
128.40, 119.32, 110.72, 77.86, 58.61 (d, J = 13.9 Hz), 41.27.
HRMS (EI+): m/z calcd for C15H20O2 [M+ – H2O]: 232.1463; found:
232.1470.
Synthesis 2009, No. 16, 2749–2755 © Thieme Stuttgart · New York