FEATURE ARTICLE
Catalytic Meerwein–Ponndorf–Verley and Oppenauer Reactions
289
MS: m/z (%) = 272 (M+), 271, 171, 131 (100%), 103, 77, 55, 41.
11-Hydroxy-2-undecanone (11c)29
IR (KBr): 3315, 2914, 2851, 1713, 1466, 1412, 1273, 1236, 1204,
HRMS: calcd for C18H24O2, 272.1776; found, 272.1792.
1167, 1126, 1069, 1022, 978, 721 cm–1.
Simultaneous Reduction/Oxidation Sequences of Hydroxy
Carbonyl Compounds with Bidentate Aluminum Catalyst 1;
General Procedure
1H NMR (CDCl3): = 3.63 (2 H, t, J = 6.3 Hz, CH2OH), 2.42 (2 H,
t, J = 7.2 Hz, COCH2), 2.14 (3 H, s, CH3), 1.41–1.66 (5 H, m, 2
CH2, OH), 1.20–1.40 (10 H, m, 5 CH2).
To a degassed solution of 2,7-dimethyl-1,8-biphenylenediol (26.5
mg, 0.125 mmol) in freshly distilled CH2Cl2 (5 mL) was added a 1
M hexane solution of Me3Al (250 L, 0.25 mmol) dropwise at r.t.
under Ar. After stirring for 0.5 h, hydroxy carbonyl compound (0.5
mmol) was added dropwise at 21 °C and the reaction mixture was
stirred for 2–12 h. The reaction was quenched with 1 N HCl and ex-
tractive work-up was performed with Et2O. The combined ethereal
extracts were dried (Na2SO4) and volatiles were evaporated. Purifi-
cation of the residual oil by column chromatography (Et2O–
CH2Cl2) afforded the corresponding hydroxy carbonyl compound.
12-Hydroxy-1-dodecen-3-one (11d)
IR (liquid film): 3431, 2930, 2855, 1684, 1618, 1466, 1402, 1080,
1059, 986, 908 cm–1.
1H NMR (CDCl3): = 6.38 (1 H, dd, J = 10.2, 17.7 Hz, C=CHCO),
6.22 (1 H, dd, J = 1.5, 17.7 Hz, CH=CCO), 5.83 (1 H, dd, J = 1.5,
10.2 Hz, CH=CCO), 3.64 (2 H, t, J = 6.6 Hz, CH2OH), 2.59 (2 H, t,
J = 7.5 Hz, COCH2), 1.59 (4 H, sept, J = 7.5 Hz, 2 CH2), 1.20–
1.45 (11 H, m, 5 CH2, OH).
13C NMR (CDCl3): = 200.97, 136.49, 127.80, 63.04, 39.67, 32.81,
29.43, 29.38, 29.25, 29.18, 25.75, 24.04.
4-(Hydroxymethyl)acetophenone (5)27
IR (liquid film): 3433, 2928, 1659, 1605, 1570, 1410, 1358, 1306,
1281, 1265, 1238, 1209, 1184, 1049, 1016, 961, 818, 687, 592
cm–1.
MS: m/z (%) = 198 (M+, 100%), 197, 141, 55.
HRMS: calcd for C12H22O2, 198.1620; found, 198.1606.
1H NMR (CDCl3): = 7.93 (2 H, d, J = 8.1 Hz, Ph), 7.45 (2 H, d,
J = 7.8 Hz, Ph), 4.76 (2 H, s, CH2OH), 2.59 (1 H, br s, OH), 2.59 (3
H, s, C-H3).
12-Hydroxy-1-phenyl-1-dodecyn-3-one (11e)
IR (liquid film): 3402, 2928, 2855, 2203, 1670, 1489, 1404, 1362,
1283, 1119, 1080, 1057, 760, 691 cm–1.
1H NMR (CDCl3): = 7.55–7.62 (2 H, m, Ph), 7.35–7.51 (3 H, m,
Ph), 3.64 (2 H, t, J = 6.6 Hz, CH2OH), 2.67 (2 H, t, J = 7.2 Hz,
COCH2), 1.74 (2 H, quint, J = 7.2 Hz, COCCH2), 1.56 (2 H, quint,
J = 6.9 Hz, CH2), 1.23–1.45 (11 H, m, 5 CH2, OH).
13C NMR (CDCl3): = 188.15, 132.92, 130.55, 128.52, 119.98,
90.54, 87.82, 63.03, 45.55, 32.80, 29.40, 29.37, 29.29, 29.00, 25.75,
24.20.
1-(4-Hydroxycyclohexyl)-2-propanone (9)28
IR (liquid film): 3400, 2930, 2856, 1709, 1452, 1420, 1362, 1277,
1165, 1086, 1051 cm–1.
1H NMR (CDCl3): = 3.99 (0.23 H, quint, J = 2.1 Hz, CHOH, cis-
isomer), 3.55 (0.77 H, tt, J = 4.2, 10.8 Hz, CHOH, trans-isomer),
2.37 (0.46 H, d, J = 6.9 Hz, COCH2, cis- isomer), 2.32 (1.54 H, d,
J = 6.6 Hz, COCH2, trans-isomer), 2.14 (0.69 H, s, CH3, cis-iso-
mer), 2.13 (2.31 H, s, CH3, trans- isomer), 1.86–2.02 (2 H, m, c-
Hex, cis- and trans-isomers), 1.18–1.86 (6 H, m, OH, c-Hex, cis-
and trans- isomers), 0.90–1.10 (2 H, m, c-Hex, cis- and trans- iso-
mers).
MS: m/z (%) = 272 (M+), 271, 171, 157, 144, 129 (100%), 102, 101,
55, 41.
HRMS: calcd for C18H24O2, 272.1776; found, 272.1806.
Tishchenko Reaction of Various Aldehydes with Bidentate
Aluminum Catalyst 3a; General Procedure
10-Hydroxydecanophenone (11a)
IR (KBr): 3329, 3057, 2914, 2851, 1684, 1598, 1580, 1466, 1447,
2,7-Dimethyl-1,8-biphenylenediol (10.7 mg, 0.05 mmol) was
placed in a dry two-neck flask with a stirring bar and freshly dis-
tilled toluene (100 L) was introduced under Ar. Then a 1 M hexane
solution of Me3Al (100 L, 0.1 mmol) was added dropwise to this
suspension at r.t. and the mixture was stirred for 0.5 h. After the sub-
sequent addition of freshly distilled i-PrOH (15.3 L, 0.2 mmol),
the solution was stirred for an additional 0.5 h. Freshly distilled al-
dehyde (10 mmol) was added slowly dropwise at 21 °C and the re-
action mixture was stirred for 0.2–5 h. The reaction was quenched
by the addition of 1 N HCl and extractive workup was performed
with Et2O. The organic extracts were washed with brine and dried
(Na2SO4). Volatiles were removed and the residual oil was purified
by column chromatography (EtOAc–hexane, 1:20) to give the cor-
responding carboxylic ester.
1410, 1377, 1213, 1105, 1059, 1003, 970, 739, 689 cm–1.
1H NMR (CDCl3): = 7.96 (2 H, m, Ph), 7.55 (1 H, m, Ph), 7.46 (2
H, m, Ph), 3.64 (2 H, m, CH2OH), 2.96 (2 H, t, J = 7.6 Hz,
PhCOCH2), 1.72 (2 H, quint, J = 7.6 Hz, PhCOCCH2), 1.16–1.62
(13 H, m, 6 CH2, OH).
13C NMR (CDCl3): = 200.43, 136.99, 132.78, 128.46, 127.97,
63.07, 38.64, 32.82, 29.47, 29.43, 29.40, 29.38, 25.75, 24.40.
MS: m/z (%) = 248 (M+), 171, 145, 120 (100%), 105, 77, 69, 55.
HRMS: calcd for C16H24O2, 248.1776; found, 248.1777.
10-Hydroxyundecanophenone (11b)
IR (KBr): 3418, 2961, 2930, 2912, 2849, 1686, 1597, 1580, 1464,
1448, 1398, 1375, 1335, 1215, 1136, 1076, 1036, 1003, 968, 932,
912, 837, 758, 741, 689 cm–1.
1H NMR (CDCl3): = 7.96 (2 H, d, J = 8.0 Hz, Ph), 7.55 (1 H, t,
J = 7.2 Hz, Ph), 7.46 (2 H, t, J = 7.6 Hz, Ph), 3.79 (1 H, m, CHOH),
2.96 (2 H, t, J = 7.2 Hz, PhCOCH2), 1.73 (2 H, quint, J = 7.2 Hz,
PhCOCCH2), 1.22–1.62 (13 H, m, 6 CH2, OH), 1.18 (3 H, d,
J = 6.4 Hz, CH3)
13C NMR (CDCl3): = 200.43, 136.99, 132.78, 128.47, 127.97,
68.17, 39.38, 38.65, 29.62, 29.48, 29.44, 29.38, 25.80, 24.40, 23.56.
MS: m/z (%) = 262 (M+), 244, 167, 133, 120 (100%), 105, 77, 55.
Cyclohexylmethyl Cyclohexylcarboxylate19b
IR (liquid film): 2932, 2855, 2669, 2341, 1733, 1450, 1391, 1371,
1313, 1246, 1194, 1171, 1134, 1038, 988, 895, 885, 843 cm–1.
1H NMR (CDCl3): = 3.87 (2 H, d, J = 6.8 Hz, CO2CH2), 2.29 (1
H, tt, J = 3.6, 11.6 Hz, CHC=O), 1.85–1.95 (2 H, m, c-Hex), 1.54–
1.80 (5 H, m, c-Hex), 1.37–1.51 (3 H, m, c-Hex), 1.12–1.35 (8 H,
m, c-Hex), 0.87–1.04 (3 H, m, c-Hex).
(3-Cyclohexenyl)methyl 3-Cyclohexenecarboxylate19b
IR (liquid film): 3024, 2918, 2841, 1736, 1653, 1454, 1439, 1391,
1373, 1306, 1223, 1167, 1063, 1045, 1016, 920, 654 cm–1.
HRMS: calcd for C17H26O2, 262.1933; found, 262.1935.
Synthesis 2002, No. 2, 279–291 ISSN 0039-7881 © Thieme Stuttgart · New York