10.1002/ejoc.201900146
European Journal of Organic Chemistry
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16.03 min (minor)]; 1H NMR (270 MHz, CDCl3) δ 3.87 (s, 2 H), 7.34–7.39
(m, 10 H).
2-Hydroxy-3-(perfluorobutyl)benzaldehyde (2a): (130.6 mg, 9%);
yellow oil; 1H NMR (270 MHz, CDCl3): δ 11.86 (s, 1 H), 9.96 (s, 1 H), 7.79
(t, J = 7.02 Hz, 1 H), 7.16 (t, J = 7.56 Hz, 1 H); 13C NMR (67.8 MHz, CDCl3):
δ 196.4, 160.8, 138.1, 136.4, 136.3, 121.4, 119.4, 117.0-120.7 (m, C4F9);
19F NMR (466 MHz, CDCl3): δ -80.8, -109.0, -122.1, -125.7; HRMS [FAB+]
m/z calcd for C11H6F9O2: 341.0224, found: 341.0239.
(Z)-2-Methyl-3-phenyloxirane (epoxide of 8)[26] : Conv. 100%, 66% ee
[The ee was determined by HPLC analysis (DAICEL CHIRALCEL OD-3
column; hexane, flow rate 0.4 mL min, tR = 10.04 min (major), tR = 11.38
min (minor)]; 1H NMR (270 MHz, CDCl3) δ 1.09 (d, J = 5.94 Hz, 3 H), 3.31-
3.38 (m, 1 H), 4.07 (d, J = 4.59 Hz, 1 H), 7.29–7.38 (m, 5 H).
2-Hydroxy-3,5-bis(perfluorobutyl)benzaldehyde (2a’): (34.0 mg, 20%);
yellow oil; 1H NMR (270 MHz, CDCl3): δ 12.21 (s, 1 H), 10.03 (s, 1 H), 8.03
(s, 1 H), 7.94 (s, 1 H); 13C NMR (67.8 MHz, CDCl3): δ 195.6, 163.2, 136.6,
134.5, 134.4, 121.2, 120.5, 120.1-110.5 (m, C4F9); 19F NMR (466 MHz,
CDCl3): δ -80.8, -109.4, -110.7, -122.1, -122.5, -125.4, -125.8; HRMS
[FAB+] m/z calcd for C15H5F18O2: 559.0002, found: 559.0014.
(E)-2-Methyl-3-phenyloxirane (epoxide of 9)[27] : Conv. 32%, 36% ee
[The ee was determined by HPLC analysis (DAICEL CHIRALCEL OD-3
column; hexane, flow rate 0.5 mL min, tR = 41.34 min (major), tR = 45.79
min (minor)]; 1H NMR (270 MHz, CDCl3) δ 1.09 (d, J = 5.94 Hz, 3 H), 3.31-
3.38 (m, 1 H), 4.07 (d, J = 4.59 Hz, 1 H), 7.29–7.38 (m, 5 H).
3-(tert-Butyl)-2-hydroxy-5-(perfluorobutyl)benzaldehyde (2b): (156.6
mg, 7%); yellow oil; 1H NMR (270 MHz, CDCl3): δ 12.14 (s, 1 H) , 9.94 (s,
1 H), 7.67 (s, 2 H), 1.44 (s, 9 H); 13C NMR (124.5 MHz, CDCl3): δ 195.6,
162.8, 138.9, 130.6, 130.0, 119.2, 118.8, 118.8-105.8 (m, C4F9), 34.2,
27.9; 19F NMR (466 MHz, CDCl3): δ -81.0, -110.3, -122.6, -125.5; HRMS
[FAB+] m/z calcd for C15H14F9O2: 396.0772, found: 396.0781.
2-Methyl-2-phenyloxirane (epoxide of 10)[27] : Conv. 83%, 48% ee [The
ee was determined by GC analysis (Agilent Cyclodex-ß, oven temp. 75 °C,
carrier gas; He), tR = 12.08 min (major), tR = 12.86 min (minor)]; 1H NMR
(270 MHz, CDCl3) δ 1.72 (s, 3 H), 2.81 (d, J = 5.13 Hz, 1 H), 2.98 (d, J =
5.40 Hz, 1 H), 7.20–7.39 (m, 5 H).
2-Hydroxy-5-nitro-3-(perfluorobutyl)benzaldehyde (2c): (23 mg, 20%);
yellow solid; mp 96 ºC; 1H NMR (270 MHz, CDCl3): δ 12.47 (br, 1 H), 10.06
(s, 1 H), 8.76 (d, J = 2.7 Hz, 1 H), 8.68 (d, J = 2.7 Hz, 1 H); 13C NMR (67.8
MHz, CDCl3): δ 195.3, 164.9, 139.9, 133.0, 131.5, 131.4, 120.5, 118.7-
111.0 (m, C4F9); 19F NMR (466 MHz, CDCl3): δ -80.8, -109.2, -121.8, -
125.7; HRMS [FAB+]: m/z calcd for C11H5F9NO4: 386.0075, found:
386.0045.
1-Phenylcyclohexene oxide (epoxide of 11)[27] : Conv. 100%, 55% ee
[The ee was determined by HPLC analysis (DAICEL CHIRALCEL OD-3
column; hexane, flow rate 0.5 mL min, tR = 26.95 min (major), tR = 31.65
min (minor)]; 1H NMR (270 MHz, CDCl3) δ 1.44-1.68 (m, 4 H), 1.94 (s, 2
H), 2.09 (s, 1 H), 2.29 (s, 1 H), 3.08 (s, 1 H), 7.31–7.39 (m, 5 H).
3-(4-Methoxyphenyl)-2,2-diphenyloxirane (epoxide of 12)[28] : Conv.
100%, 60% ee [The ee was determined by HPLC analysis (DAICEL
CHIRALCEL OD-3 column; hexane/iPrOH = 99 : 1, flow rate 0.4 mL min,
tR = 14.01 min (major), tR = 21.02 min (minor)]; 1H NMR (270 MHz, CDCl3)
δ 3.73 (s, 3 H), 4.26 (s, 1 H), 6.68 (d, J = 8.64 Hz, 2 H), 6.93 (d, J = 8.64
Hz, 2 H), 7.26–7.35 (m, 10 H).
2-Hydroxy-5-methoxy-3-(perfluorobutyl)benzaldehyde (2d): (163.3
mg, 23%); yellow solid; mp 51 ºC; 1H NMR (270 MHz, CDCl3): δ 11.35 (s,
1 H), 9.91 (s, 1 H), 7.34 (d, J = 3.24 Hz, 1 H), 7.26 (d, J = 3.24 Hz, 1 H),
3.86 (s, 3 H); 13C NMR (67.8 MHz, CDCl3): δ 195.9, 154.8, 152.0, 123.6,
123.5, 121.3, 121.0, 117.7-109.3 (m. C4F9), 56.2; 19F NMR (466 MHz,
CDCl3): δ -80.8, -108.9, -122.1, -125.8; HRMS [FAB+]: m/z calcd for
C12H8F9O3: 371.0330, found: 371.0332.
2-(4-Fluorophenyl)-3-phenyloxirane (epoxide of 13)[29] : Conv. 56%,
38% ee [The ee was determined by HPLC analysis (DAICEL CHIRALCEL
OD-3 column; hexane/iPrOH = 9 : 1, flow rate 0.4 mL min, tR = 9.79 min
1
(major), tR = 11.93 min (minor)]; H NMR (270 MHz, CDCl3) δ 3.84 (dd, J
5-(tert-Butyl)-2-hydroxy-3-(perfluorobutyl)benzaldehyde (2e): (156.6
mg, 71%); yellow oil; 1H NMR (270 MHz, CDCl3): δ 11.64 (s, 1 H), 9.95 (s,
1 H), 7.75 (q, J = 4.05 Hz, 2 H), 1.36 (s, 9 H); 13C NMR (67.8 MHz, CDCl3):
δ 196.6, 158.6, 142.6, 134.6, 133.7, 133.6, 121.0, 118.7-108.9 (m, C4F9),
34.3, 31.1; 19F NMR (466 MHz, CDCl3): δ -80.8, -108.9, -122.3, -125.8;
HRMS [FAB+]: m/z calcd for C15H13O2F9: 397.0850, found: 397.0862.
= 1.62, 7.02 Hz, 2 H), 7.06–7.35 (m, 9 H).
Typical procedure for perfluoroalkylation of salicylaldehyde: To a
suspension of salicylaldehyde and cesium carbonate (4-8 eq.) in DMF (10
mL) was added perfluorobutyl iodide (3-10 eq.). The mixture was stirred
for 15 min - 20 h at 23 - 80 ºC in oil bath. The mixture was quenched with
1 M aq. HCl. After the addition of diethyl ether, the organic phase was
separated and the aqueous phase was extracted with diethyl ether. The
combined organic phase was washed with brine, dried over Na2SO4,
filtered, and evaporated. The residue was purified by column
chromatography on silica gel to give perfluoroalkylated compound.
5-(tert-Butyl)-2-hydroxy-3-(perfluorooctyl)benzaldehyde (2f): (182.0
mg, 57%); yellow solid; mp 48 ºC; 1H NMR (270 MHz, CDCl3): δ 11.65 (s,
1 H), 9.95 (s, 1 H), 7.75 (q, J = 4.59 Hz, 2 H), 1.36 (s, 9 H); 13C NMR (124.5
MHz, CDCl3): δ 196.7, 158.7, 142.7, 134.6, 133.8, 133.7, 121.1, 118.4-
106.2 (m, C4F9), 34.4, 31.1; 19F NMR (466 MHz, CDCl3): δ -80.6, -108.7, -
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