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Organic & Biomolecular Chemistry
Page 4 of 6
DOI: 10.1039/C5OB01730K
ARTICLE
Journal Name
parts per million downfield from tetramethylsilane and are
3ꢀ(4ꢀfluorophenyl)ꢀ1,3ꢀdiphenylpropanꢀ1ꢀone (3ea).13 White
referenced to residual protium in the NMR solvent (CHCl3 = δ solid, 90% yield, m.p. = 95.3ꢀ97.2 oC. 1H NMR (600 MHz, CDCl3) δ
7.26). Carbon nuclear magnetic resonance (13C NMR) spectra 7.94 (dd, J = 8.4, 1.2 Hz, 2 H), 7.58ꢀ7.55 (m, 1 H), 7.47ꢀ7.44 (m, 2
were recorded on a Bruker 151 MHz spectrometer. Chemical H), 7.29 ꢀ7.22 (m, 7 H), 6.98ꢀ 6.95 (m, 2 H), 4.83 (t, J = 7.3 Hz, 1
shifts for carbon are reported in parts per million downfield H), 3.76ꢀ3.69 (m, 2 H).13C NMR (151 MHz, CDCl3) δ 197.9, 161.4
from tetramethylsilane and are referenced to the carbon (d, J = 244.7 Hz), 144.1, 139.9, 137.1, 133.2, 129.4, 128.7, 128.1 (d,
resonances of the solvent (CDCl3 = δ 77.07). Data are J = 2.9 Hz), 127.8, 127.7, 126.6, 115.4 (d, J = 21.3 Hz), 45.2, 44.8.
represented as follows: chemical shift, multiplicity (s = singlet,
3ꢀ(4ꢀchlorophenyl)ꢀ1,3ꢀdiphenylpropanꢀ1ꢀone (3fa).14 White
d = doublet, t = triplet, q = quartet, m = multiplet), coupling solid, 93% yield, m.p. = 85.2ꢀ86.0 oC. 1H NMR (600 MHz, CDCl3) δ
constants in Hertz (Hz), integration. Benzhydryl alcohols 11 and 7.92 (d, J = 7.6 Hz, 2 H), 7.55 (t, J = 7.3 Hz, 1 H), 7.44 (t, J = 7.7
12
βꢀketo acids
were synthesized according to reported Hz, 2 H), 7.29ꢀ7.17 (m, 9H), 4.80 (t, J = 7.2 Hz, 1 H), 3.70 (dd, J =
mass 7.2, 4.4 Hz, 2 H). 13C NMR (151 MHz, CDCl3) δ 197.7, 143.8,
spectra (ESIꢀHRMS) were recorded on a Bruke PꢀSIMSꢀGly 142.7, 137.0, 133.3, 132.2, 129.3, 128.7, 128.7, 128.1, 127.8, 126.7,
procedures. Electrospray ionization highꢀresolution
FTꢀICR mass spectrometer.
45.3, 44.6.
3ꢀ(4ꢀbromophenyl)ꢀ1,3ꢀdiphenylpropanꢀ1ꢀone (3ga).15 White
solid, 90% yield, m.p. = 101.1ꢀ102.1 oC. 1H NMR (600 MHz,
CDCl3) δ 7.93 (d, J = 7.9 Hz, 2 H), 7.56 (t, J = 7.1 Hz, 1 H), 7.45 (t,
J = 7.6 Hz, 2 H), 7.38 (d, J = 8.1 Hz, 2 H), 7.28 (t, J = 7.4 Hz, 2 H),
7.23 (d, J = 7.7 Hz, 2 H), 7.19 (t, J = 7.3 Hz, 1 H), 7.14 (d, J = 8.1
Hz, 2 H), 4.79 (t, J = 7.2 Hz, 1 H), 3.72ꢀ3.70 (m, 2H). 13C NMR
(151 MHz, CDCl3) δ 197.7, 143.7, 143.27, 136.97, 133.3, 131.7,
129.7, 128.7, 128.7, 128.1, 127.8, 126.7, 120.3, 45.4, 44.5.
3ꢀ(4ꢀmethoxyphenyl)ꢀ1,3ꢀdiphenylpropanꢀ1ꢀone(3ha).13 White
solid, 96% yield, m.p. = 91.5ꢀ92.5 oC. 1H NMR (600 MHz, CDCl3) δ
7.94 (dd, J = 8.3, 1.1 Hz, 2 H), 7.55 (t, J = 7.4 Hz, 1 H), 7.44 (t, J =
7.8 Hz, 2 H), 7.28ꢀ7.25 (m, 4 H), 7.19ꢀ7.17 (m, 3 H), 6.82ꢀ6.81 (m, 2
H), 4.79 (t, J = 7.3 Hz, 1 H), 3.76 (s, 3 H), 3.71 (dd, J = 7.3, 1.7 Hz,
2 H). 13C NMR (151 MHz, CDCl3) δ 198.2, 158.1, 144.6, 137.2,
136.3, 133.1, 128.8, 128.7, 128.6, 128.1, 127.8, 126.4, 114.0, 55.3,
45.2, 45.0.
Typical procedure for I2ꢀcatalyzed decarboxylative
substitution of βꢀketo acids with benzylic alcohols.
A 25 mL Schlenk flask, fitted with a reflux condenser, I2 (0.05
mmol, 10 mol %), benzylic alcohol
1 (0.5 mmol), βꢀketo acid 2
(0.6 mmol) and 3 mL CH3NO2. The mixture was heated at 70
oC for 2ꢀ6 h, cooled down, and treated with aqueous Na2S2O3,
then extracted three times with ethyl acetate. The combined
organic extracts were dried with anhydrous Na2SO4. After
concentration under reduced pressure, the resulting residue was
purified by column chromatography (SiO2; Hexane/EtOAc,
20:1) to give propargylic alkylation product
3.
1,3,3ꢀtriphenylpropanꢀ1ꢀone (3aa).13 White solid, 92% yield,
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m.p. = 93.2ꢀ94.2 C. H NMR (600 MHz, CDCl3) δ 7.94 (d, J = 7.8
Hz, 2 H), 7.55 (t, J = 7.3 Hz, 1 H), 7.45 (t, J = 7.7 Hz, 2 H), 7.28 (s,
4 H), 7.27 (s, 4 H),7.18 (m, 2 H), 4.84 (t, J = 7.2 Hz, 1 H), 3.75 (d, J
= 7.3 Hz, 2 H). 13C NMR (151 MHz, CDCl3) δ 198.0, 144.2, 137.1,
133.1, 128.7, 128.6, 128.1, 127.9, 126.4, 46.0, 44.8.
3ꢀ(3ꢀmethoxyphenyl)ꢀ1,3ꢀdiphenylpropanꢀ1ꢀone (3ia).14 White
solid, 90% yield, m.p. = 85.1ꢀ86.5 oC. 1H NMR (600 MHz, CDCl3) δ
7.93 (d, J = 7.2 Hz, 2 H), 7.53 (d, J = 6.8 Hz, 1 H), 7.43 (t, J = 7.1
Hz, 2 H), 7.26 (s, 4H), 7.20ꢀ7.17 (m, 2H), 6.86 (d, J = 7.0 Hz, 1 H),
6.81 (s, 1 H), 6.71 (d, J = 7.4 Hz, 1H), 4.80 (t, J = 6.5 Hz, 1H), 3.74ꢀ
3.71 (m, 5H). 13C NMR (151 MHz, CDCl3) δ 198.0, 159.8, 145.9,
144.1, 137.1, 133.1, 129.6, 128.7, 128.1, 127.9, 126.5, 120.3, 114.2,
111.4, 55.2, 46.0, 44.7.
3ꢀ(naphthalenꢀ2ꢀyl)ꢀ1,3ꢀdiphenylpropanꢀ1ꢀone (3ja).14 White
solid, 93% yield, m.p. = 125.1ꢀ126.1 oC. 1H NMR (600 MHz,
CDCl3) δ 7.95 (d, J = 7.4 Hz, 2 H), 7.76ꢀ7.71 (m, 4 H), 7.54 (t, J =
7.4 Hz, 1 H), 7.45ꢀ7.42 (m, 5H), 7.30ꢀ7.25 (m, 4 H), 7.17 (t, J = 7.2
Hz, 1 H), 5.00 (t, J = 7.2 Hz, 1H), 3.88ꢀ3.79 (m, 2 H). 13C NMR
(151 MHz, CDCl3) δ 198.0, 144.0, 141.6, 137.1, 133.5, 133.1, 132.2,
128.6, 128.6, 128.3, 128.1, 128.0, 127.8, 127.6, 126.8, 126.5, 126.0,
125.8, 125.6, 46.0, 44.6.
1,3ꢀdiphenylꢀ3ꢀ(pꢀtolyl)propanꢀ1ꢀone (3ba).13 White solid, 94%
yield, m.p. = 95.5ꢀ96.5 oC. 1H NMR (600 MHz, CDCl3) δ 7.94 (d, J
= 7.7 Hz, 2 H), 7.55 (t, J = 7.0 Hz, 1 H), 7.44 (t, J = 7.2 Hz, 2 H),
7.27ꢀ7.26 (m, 4 H), 7.16 (d, J = 5.8 Hz, 3 H), 7.09 (d, J = 6.9 Hz, 2
H), 4.80 (t, J = 6.9 Hz, 1 H), 3.73 (d, J = 7.1 Hz, 2 H), 2.29 (s, 3 H).
13C NMR (151 MHz, CDCl3) δ 198.1, 144.5, 141.2, 137.2, 135.9,
133.1, 129.3, 128.6, 128.6, 128.1, 127.9, 127.8,126.4, 45.6, 44.9,
21.1.
1,3ꢀdiphenylꢀ3ꢀ(mꢀtolyl)propanꢀ1ꢀone (3ca).14 White solid, 91%
yield, m.p. = 72.5ꢀ73.2 oC. 1H NMR (600 MHz, CDCl3) δ 7.94 (d, J
= 7.7 Hz, 2 H), 7.55 (t, J = 7.0 Hz, 1 H), 7.44 (t, J = 7.2 Hz, 2 H), 1H
NMR (600 MHz, CDCl3) δ 7.93 (d, J = 7.5 Hz, 2 H), 7.54 (t, J = 7.3
Hz, 1H), 7.43 (t, J = 7.6 Hz, 2H), 7.26ꢀ7.25 (m, 4 H), 7.15 (t, J = 7.3
Hz, 2 H), 7.06 (d, J = 7.8 Hz, 2 H), 6.98 (d, J = 7.3 Hz, 1 H), 4.78 (t,
J = 7.2 Hz, 1 H), 3.72 (dd, J = 7.2, 2.1 Hz, 2 H), 2.29 (s, 3H). 13
C
3ꢀ(4ꢀmethoxyphenyl)ꢀ3ꢀphenylꢀ1ꢀ(pꢀtolyl)propanꢀ1ꢀone (3hb).
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White solid, 84% yield, m.p. = 80.7ꢀ81.7 C. H NMR (600 MHz,
CDCl3) δ 7.83 (d, J = 8.2 Hz, 2 H), 7.26ꢀ7.22 (m, 6 H), 7.18ꢀ7.15
(m, 3 H), 6.80 (d, J = 8.7 Hz, 2 H), 4.77 (t, J = 7.3 Hz, 1 H), 3.75 (s,
3 H), 3.67 (dd, J = 7.3, 2.0 Hz, 2 H), 2.40 (s, 3 H). 13C NMR (151
MHz, CDCl3) δ 197.8, 158.0, 144.6, 143.9, 136.4, 134.7, 129.3,
128.8, 128.5, 128.2, 127.8, 126.3, 113.9, 55.2, 45.2, 44.8, 21.6.
HRMS calc. for [MꢀH]ꢀ C23H21O2: 329.1542, found: 329.1532.
1ꢀ(4ꢀfluorophenyl)ꢀ3ꢀ(4ꢀmethoxyphenyl)ꢀ3ꢀphenylpropanꢀ1ꢀ
NMR (151 MHz, CDCl3) δ 198.1, 144.3, 144.2, 138.2, 137.2, 133.1,
128.8, 128.6, 128.6,128.5, 128.1, 127.9, 127.3, 126.4, 124.8, 45.99,
44.81, 21.58.
1,3ꢀdiphenylꢀ3ꢀ(oꢀtolyl)propanꢀ1ꢀone (3da).13 White solid, 94%
yield, m.p. = 89.2ꢀ90.2 oC. 1H NMR (600 MHz, CDCl3) δ 7.92 (d, J
= 7.4 Hz, 2 H), 7.54 (t, J = 7.4 Hz, 1 H), 7.43 (t, J = 7.7 Hz, 2 H),
7.26ꢀ7.20 (m, 5 H), 7.17ꢀ7.10 (m, 4 H), 5.02 (t, J = 7.2 Hz, 1 H),
3.71 (qd, J = 17.2, 7.3 Hz, 2 H), 2.33 (s, 3 H). 13C NMR (151 MHz,
CDCl3) δ 198.1, 143.8, 141.9, 137.2, 136.5, 133.1, 130.8, 128.6,
128.5, 128.1, 128.1, 126.4, 126.3, 126.1, 45.1, 41.9, 20.0.
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one (3hc). White solid, 75% yield, m.p. = 75.5ꢀ76.5 C. H NMR
(600 MHz, CDCl3) δ 7.95 (dd, J = 8.8, 5.4 Hz, 2 H), 7.28ꢀ7.23 (m, 2
4 | J. Name., 2012, 00, 1-3
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