Selective oxidation of alcohols at the benzylic position by benzeneseleninic anhydride

Article abstract of DOI:10.1248/cpb.52.1009

Benzeneseleninic anhydride in the presence of tert-butyl hydroperoxide in chlorobenzene at about 70°C is an effective oxidizing agent for the selective oxidation of alcohols at the benzylic position.

Full text of DOI:10.1248/cpb.52.1009

August 2004
Notes
Chem. Pharm. Bull. 52(8) 1009—1012 (2004)
1009
Selective Oxidation of Alcohols at the Benzylic Position by
Benzeneseleninic Anhydride
Naotoshi TOKI and Tsuyoshi SATOH*
Department of Chemistry, Faculty of Science, Tokyo University of Science; Kagurazaka, Shinjuku-ku, Tokyo 162–8601,
Japan. Received April 5, 2004; accepted May 25, 2004
Benzeneseleninic anhydride in the presence of tert-butyl hydroperoxide in chlorobenzene at about 70 °C is
an effective oxidizing agent for the selective oxidation of alcohols at the benzylic position.
Key words oxidation; selective oxidation; benzeneseleninic anhydride; benzyl alcohol
Oxidation of alcohols to aldehydes and ketones is obvi- 3 eq of 2-methyl-2-propanol instead of TBHP (entry 4) a
ously one of the most fundamental transformations in syn- similar result was obtained. From these results, about 3 eq of
thetic organic chemistry and innumerable methods have been TBHP was found to be essential for the selective oxidation,
developed.1,2) One interesting objective in the oxidation of al- though the real reason is obscure at present. To rule out the
cohols is the selective oxidation in polyhydroxylated mole- possibility that the selective oxidation takes place only by
cules. Many methods for selective oxidation of primary and TBHP, the reaction was carried out in the presence of 3 eq of
secondary hydroxy groups have been reported.3—11) Selective TBHP without BSA (entry 6). No oxidation at all was ob-
oxidation of benzyl and allyl alcohols is also known.12—14)
Benzeneseleninic anhydride (BSA) is easily prepared from
diphenyl diselenide by oxidation with ozone or tert-butyl hy-
droperoxide (TBHP)15) and is now commercially available.16)
Barton initially used BSA as an oxidizing agent for oxidation
of phenols,17) oxidation of ketones to enones,18) regeneration
of ketones from hydrazones, oximes, semicarbazones,19) and
thioacetals.20) BSA was also reported to be an oxidant for al-
cohols to carbonyl compounds.21)
served under these conditions.
Further, we investigated this chemoselective oxidation
Table 1. Chemoselective Oxidation of Primary and Secondary Alcohols
with BSA
We previously reported an angular hydroxylation of poly-
cyclic ketones using BSA.22,23) In continuation of our interest
in BSA as an oxidizing agent, we recently found that BSA is
an effective oxidant for selective oxidation of alcohols at the
benzylic position.
3
4
TBHP Temperature
Time
(h)
Entry
(eq)
(°C)
Yield %
Yield %
To investigate the effect of BSA as a selective oxidizing
agent, we first treated a mixture of secondary alcohol 1 (1 eq)
and primary alcohol 2 (1 eq) with 1 eq of BSA in chloroben-
zene at 50 °C for 3 h (see Table 1; entry 1). Only ketone 3
was obtained in 34% yield with recovery of the alcohols and
no aldehyde 4 was obtained. This result implied that selective
oxidation of primary and secondary alcohols could be possi-
ble.
1
2
3
4
0
5
5
3
50
50
70
70
3
3
1.5
1.5
34
66
90
89
0
Trace
Trace
Trace
Table 2. Chemoselective Oxidation of 1-Phenyldodecane-1,12-diol with
BSA
Encouraged by this result, we further studied this oxida-
tion and found that TBHP is effective for the selective oxida-
tion of alcohols with BSA. As shown in entry 2, the presence
of 5 eq of TBHP gave a much higher yield of the ketone 3.
When this reaction was carried out at 70 °C the yield of the
ketone 3 was increased up to 90% within 1.5 h (entry 3).
Even under these conditions only a trace of aldehyde 4 was
obtained. Later, 3 eq of TBHP was found to be enough in this
selective oxidation (entry 4).
Next, we studied chemoselective oxidation of primary and
secondary alcohols using diol 5 as an example (see Table 2).
Under the best conditions mentioned above (Table 1; entry
4), the diol 5 was oxidized to ketoalcohol 6 in 82% yield
without ketoaldehyde 7 (Table 2; entry 1). When the amount
of TBHP was reduced to 1 eq, a considerable amount of the
ketoaldehyde 7 was obtained (entry 2). In the case of the ab-
sence of TBHP (entry 3), the result was quite similar to the
6
7
BSA
(eq)
TBHP
(eq)
Entry
Yield %
Yield %
1
2
3
4
5
6
1
1
1
1
0.5
0
3
1
0
82
67
69
70
82
0b)
0
21
18
17
3.5
0
a)
—
3
3
a) tert-BuOH (3 eq) was added to the reaction mixture instead of TBHP. b) No re-
result in entry 2. When this reaction was carried out with action was observed.
* To whom correspondence should be addressed. e-mail: tsatoh@ch.kagu.tus.ac.jp
© 2004 Pharmaceutical Society of Japan

1010
Vol. 52, No. 8
Table 3. Chemoselective Oxidation of Several Diols with BSA
8
9
10
Entry
Chart 2. Oxidation of 4-(1-Hydroxyethyl)benzyl Alcohol with BSA in the
Presence of TBHP
R
n
Yield %
Yield %
Experimental
1
2
3
4
5
6
3
9a
9b
9c
9d
9e
9f
79
0
1
All melting points are uncorrected. H-NMR spectra were measured in a
CDCl3 solution with JEOL JNM-LA 400 and 500 spectrometer. Electron-
impact mass spectra (MS) were obtained at 70 eV by direct insertion. Silica
gel 60 (MERCK) containing 0.5% fluorescence reagent 254 and a quartz
column were used for column chromatography and the products having UV
absorption were detected by UV irradiation. In experiments requiring a dry
reagent and solvent, chlorobenzene, DMSO, CH2Cl2 were distilled from
CaH2 and THF was distilled from diphenylketyl. TBHP (MERCK, 80% so-
lution in di-tert-butylperoxide) was used without any purification.
Chemoselective Oxidation of Secondary Alcohol 1 and Primary Alco-
hol 2 with BSA To a solution of BSA (180 mg; 0.5 mmol) in 15 ml of
chlorobenzene at 70 °C was added a solution of 1-phenyl-1-heptanol 1
(96 mg; 0.5 mmol) and 4-phenylbutanol 2 (75 mg; 0.5 mmol) in 0.5 ml of
chlorobenzene. To the mixture was added TBHP (0.19 ml; 1.5 mmol) and the
reaction mixture was stirred at 70 °C for 90 min. The reaction was quenched
by sat. Na2S2O3 and the whole was extracted with benzene. The organic
layer was washed with water and brine, and then dried over MgSO4. The
product was purified by silica gel column chromatography to give 1-phenyl-
1-heptanone (heptanophenone) 3 (85 mg; 89%) and recovery of alchol 2
(48 mg; 64%).
10
10
10
10
10
72
67
46
51
16
10b 15
10c 16
10d 34
10e 32
a)
—
a) A complex mixture was obtained from this reaction.
Chart 1. Intramolecular Chemoselective Oxidation of 1-Phenyl-1,3-bu-
tanediol with BSA in the Presence of TBHP
1-Phenyldodecane-1,12-diol (5) To a solution of PPTS (503 mg; 2.0
mmol) in 100 ml of dry CH2Cl2 at 0 °C were added 1,12-dodecanediol
(4.04 g; 20 mmol) and dihydropyran (1.85 g; 22 mmol) and the reaction mix-
ture was stirred at room temperature for 30 min. The mixture was diluted
with Et2O and the solution was washed with brine. The product was purified
by silica gel column chromatography to give mono-protected alcohol
(2.97 g; 52%) as a colorless oil. IR (neat) 3400 (OH), 2927, 2855, 1466,
1353, 1201, 1137, 1122, 1078, 1034 cmꢀ1; 1H-NMR d 1.20—1.75 (26H, m),
with various kinds of diols and the results are shown in Table
3. As shown in entry 1 to entry 3, benzylic secondary alco-
hols 8a—c were selectively oxidized to ketones though the
selectivity was somewhat lower when R are 4-chlorophenyl
or 4-methylphenyl (entries 2, 3). The results shown in entries 3.34—3.42 (1H, m), 3.47—3.53 (1H, m), 3.61—3.66 (2H, m), 3.69—3.77
(1H, m), 3.84—3.91 (1H, m), 4.58 (1H, t, Jꢁ3.5 Hz).
4 and 5 indicated that secondary alcohols at the non-benzylic
position showed low selectivity. In the case of allylic alcohol
8f, BSA was not useful for the oxidation (entry 6). In all the
reactions aldehyde 11 was not obtained.
To a solution of oxalyl chloride (0.4 ml; 4.56 mmol) in 45 ml of CH2Cl2
was added DMSO (0.66 ml; 9.29 mmol) at ꢀ78 °C. After 10 min, a solution
of the mono-protected alcohol (1.3 g; 4.65 mmol) in CH2Cl2 was added, and
the mixture was stirred for 15 min at ꢀ60 °C. Triethylamine (23.2 mmol)
was added to the reaction mixture, and the reaction mixture was stirred for
15 min at room temperature. The reaction was quenched by sat. NH4Cl and
the whole was extracted with CHCl3. The product was purified by silica gel
column chromatography to give aldehyde (1.15 g; 89%) as a colorless oil. IR
(neat) 2928, 2855, 2716, 1727 (CHO), 1466, 1353, 1201, 1137, 1122, 1078,
Next, diol 12, which has two secondary alcohols, one of
which is at the benzylic position, was synthesized and the ox-
idation with BSA in the presence of 3 eq of TBHP at 70 °C
was carried out. After 1.5 h, the reaction was quenched and
we obtained the ketoalcohol 13 in 79% yield. From this reac-
tion 16% of the starting diol 12 was recovered; however, no
diketone was observed.
Finally, we investigated the selectivity for primary and sec-
ondary benzyl alcohols (Chart 2). 4-(1-Hydroxyethyl)benzyl
alcohol 14 was oxidized under the same conditions described
above and the reaction was stopped after 15 min. As shown
in Chart 2, the aldehyde 15 was obtained in 55% yield with
keto-alcohol 16 (14%). This result indicated that the speed of
the oxidation of primary benzyl alcohol with BSA-TBHP is
much faster than that for the secondary benzyl alcohol.
In conclusion, we have found that BSA in the presence of
3 eq of TBHP in chlorobenzene at 70 °C is effective oxidiz-
ing agent for selective oxidation of benzyl alcohols to ke-
tones and aldehydes.
1034, 988 cmꢀ1; H-NMR d 1.27—1.86 (24H, m), 2.40—2.44 (2H, dt, Jꢁ
1
7.5, 1.9 Hz), 3.36—3.40 (1H, m), 3.48—3.52 (1H, m), 3.71—3.75 (1H, m),
3.85—3.89 (1H, m), 4.57 (1H, t, Jꢁ4.6 Hz), 9.76 (1H, t, Jꢁ1.9 Hz).
To a solution of PhMgBr (1.58 mmol) in THF (10 ml) was added the alde-
hyde (298 mg; 1.05 mmol) at 0 °C. After the mixture was stirred for 1 h at
room temperature, the reaction was quenched with sat. NH4Cl and the whole
was extracted with AcOEt. The product was purified by silica gel column
chromatography to give alcohol (341 mg; 91%) as a colorless oil. IR (neat)
3437 (OH), 2927, 2854, 1455, 1136, 1121, 1077, 1024, 701 cmꢀ1; 1H-NMR
d 1.25—1.86 (26H, m), 3.35—3.40 (1H, m), 3.47—3.51 (1H, m), 3.70—
3.74 (1H, m), 3.84—3.89 (1H, m), 4.57 (1H, t, Jꢁ3.7 Hz), 4.64—4.68 (1H,
m), 7.23—7.35 (5H, m).
To a solution of the alcohol (341 mg; 0.95 mmol) in EtOH (9 ml) was
added PPTS (23.8 mg; 0.09 mmol). The mixture was stirred for 2 h at 60 °C.
After removal of the solvent, the product was purified by silica gel column
chromatography to give diol 5 (212 mg; 81%) as colorless crystals; mp
43.5—44.5 °C (AcOEt–hexane). IR (KBr) 3307 (OH), 2919, 2849, 1468,
1054, 763, 700 cmꢀ1 1H-NMR d 1.25—1.88 (20H, m), 3.63 (2H, t, Jꢁ
.
6.3 Hz), 4.66 (1H, t, Jꢁ6.3 Hz), 7.25—7.36 (5H, m). MS m/z (%) 278 (Mꢂ,

August 2004
1011
0.6), 120 (15), 107 (100), 105 (14), 79 (9), 77 (8). Calcd for C18H30O2: M,
hexyl-12-hydroxy-1-dodecanone 9e: Colorless oil. IR (neat) 3435 (OH),
1
278.2247. Found: m/z 278.2245. Anal. Calcd C18H30O2: C, 77.65; H, 10.86. 2928, 2852, 1702 (CO), 1471, 1382, 1057, 718 cmꢀ1; H-NMR d 1.19—
Found: C, 77.81; H, 10.86.
12-Hydroxy-1-phenyl-1-dodecanone (6) To a solution of BSA (90 mg;
1.36 (24H, m), 1.53—1.83 (4H, m), 2.27—2.36 (1H, m), 2.42 (2H, t, Jꢁ
7.3 Hz), 3.63 (2H, t, Jꢁ6.7 Hz). FAB-MS m/z 283 ([MꢂH]ꢂ), 265, 199,
0.25 mmol) in 3 ml of chlorobenzene at 70 °C was added a solution of 5 181, 137, 83. 15-Hydroxypentadec-2-en-4-one 9f: Colorless oil. IR (neat)
1
(69.5 mg; 0.25 mmol) in 1.0 ml of chlorobenzene and TBHP (0.094 ml;
0.75 mmol), and the reaction mixture was stirred at 70 °C for 90 min. The re-
3356 (OH), 2916, 2849, 1685 (CO), 1447, 1063, 730, 688 cmꢀ1; H-NMR
d 1.28—1.66 (18H, m), 1.90 (3H, dd, Jꢁ6.7, 1.6 Hz), 2.51(2H, t, Jꢁ7.5 Hz),
action was quenched by sat. Na2S2O3, and the whole was extracted with ben- 3.64 (2H, t, Jꢁ6.5 Hz), 6.12 (1H, dq, Jꢁ15.9, 1.6 Hz), 6.84 (1H, dq,
zene. The organic layer was washed with water and brine, and the product
was purified by silica gel column chromatography to give ketone 6 (56 mg;
Jꢁ15.9, 6.7 Hz). FAB-MS m/z 241 ([MꢂH]ꢂ), 209, 199, 148, 132, 104,
102, 69.
82%) as a colorless oil. IR (neat) 3356 (OH), 2916, 2849, 1685 (CO), 1464,
Keto-aldehyde (10b—e) 12-(4-Chlorophenyl)-12-oxododecanal 10b:
1
1447, 1377, 1207, 1063, 730, 688, 542 cmꢀ1; H-NMR d 1.26—1.76 (18H, Colorless oil. IR (neat) 2915, 2849, 1715 (CHO), 1681 (CO), 1590, 1463,
m), 2.96 (2H, t, Jꢁ7.7 Hz), 3.64 (2H, t, Jꢁ6.7 Hz), 7.44—7.97 (5H, m). MS
m/z (%) 276 (Mꢂ, 14), 120 (100), 105 (66), 77 (16). Calcd for C18H28O2: M,
276.2089. Found: m/z 276.2088. 12-Oxo-12-phenyldodecanal 7 was ob-
tained as by-product in entry 2—5, Table 2. Colorless oil. IR (neat) 2916,
2850, 2725, 1717 (CHO), 1680 (CO), 1450, 1366, 1211, 737, 688 cmꢀ1; 1H-
1099, 999 cmꢀ1 1H-NMR d 1.25—1.29 (12H, m), 1.54—1.75 (4H, m),
;
2.40—2.44 (2H, m), 2.91—2.94 (2H, m), 7.43 (2H, d, Jꢁ6.8 Hz), 7.90 (2H,
d, Jꢁ6.8 Hz), 9.77 (1H, t, Jꢁ1.8 Hz). FAB-MS m/z 309 ([MꢂH]ꢂ), 221,
185, 136, 92. 12-(4-Methylphenyl)-12-oxododecanal 10c: Colorless oil. IR
1
(neat) 2916, 2850, 1718 (CHO), 1681 (CO), 1464, 801 cmꢀ1; H-NMR d
NMR d 1.29—1.76 (16H, m), 2.40—2.43 (2H, m), 2.95—2.98 (2H, m), 1.25—1.36 (12H, m), 1.59—1.75 (4H, m), 2.41 (3H, s), 2.42 (2H, dt, Jꢁ7.3,
7.44—7.97 (5H, m), 9.76 (1H, t, Jꢁ1.9 Hz). MS m/z (%) 274 (Mꢂ, 4), 133 1.9 Hz), 2.93 (2H, t, Jꢁ7.3 Hz), 7.25 (2H, d, Jꢁ8.6 Hz), 7.86 (2H, d, Jꢁ
(14), 120 (100), 105 (84), 77 (26). Calcd for C18H26O2: M, 274.1937. Found: 8.6 Hz), 9.76 (1H, t, Jꢁ1.6 Hz). FAB-MS m/z 289 ([MꢂH]ꢂ), 255, 197,
m/z 274.1932.
Diols 8a—f Diols in Table 3 were synthesized in a similar manner to 2916, 2849, 1714 (CHO, CO), 1462, 1414, 1084, 699 cmꢀ1
that described above. 1-Phenyl-1,5-pentanediol 8a: Colorless oil; IR (neat) 1.22—1.28 (14H, m), 1.52—1.64 (4H, m), 2.39—2.44 (4H, m), 3.68 (2H,
3340 (OH), 2938, 2864, 1454, 1055, 1028, 761, 701 cmꢀ1
173, 136, 91. 12-Oxo-13-phenyltridecanal 10d: Colorless oil. IR (neat)
;
1H-NMR d
;
1H-NMR d s), 7.19—7.34 (5H, m), 9.76 (1H, t, Jꢁ1.9 Hz). FAB-MS m/z 289 ([Mꢂ
1.22—1.86 (6H, m), 3.62 (2H, t, Jꢁ6.4 Hz), 4.67 (1H, t, Jꢁ6.4 Hz), 7.25— H]ꢂ), 273, 221, 147, 118, 72. 12-Cyclohexyl-12-oxododecanal 10e: Color-
7.34 (5H, m). MS m/z (%) 180 (Mꢂ, 10), 108 (8), 107 (100), 79 (36), 77 less oil IR (neat) 2930, 2852, 2725, 1719 (CHO), 1698 (CO), 1471, 1410,
(17). Calcd for C11H16O2: M, 180.1143. Found: m/z 180.1149. 1-(4- 1387, 1148, 1082, 1002 cmꢀ1; 1H-NMR d 1.15—1.36 (18H, m), 1.52—1.57
Chlorophenyl)dodecane-1,12-diol 8b: Colorless crystals; mp 64.5—65.5 °C
(2H, m), 1.59—1.68 (2H, m), 1.74—1.83 (4H, m), 2.29—2.36 (1H, m),
(AcOEt–hexane). IR (KBr) 3271 (OH), 2918, 2849, 1492, 1463, 1052, 2.40—2.44 (4H, m), 9.76 (1H, t, Jꢁ1.5 Hz). FAB-MS m/z 281 ([MꢂH]ꢂ),
827 cmꢀ1; H-NMR d 1.25—1.87 (20H, m), 3.63 (2H, m), 4.65 (1H, m), 221, 197, 135, 83, 73.
1
7.26—7.32 (4H, m). MS m/z (%) 312 (Mꢂ, trace), 277 (12), 141 (100), 77
3-Hydroxy-1-phenyl-1-butanone (13) Colorless oil. IR (neat) 3421
(13). Calcd for C18H29ClO2: M, 312.1859. Found: m/z 312.1855. Anal. (OH), 2971, 1682 (CO), 1598, 1449, 1374, 1283, 1214, 754, 690, 500 cmꢀ1
Calcd: C, 69.10; H, 9.34; Cl, 11.33. Found: C, 69.29; H, 9.38; Cl, 11.25. 1- 1H-NMR d 1.31 (3H, d, Jꢁ6.5 Hz), 3.05 (1H, dd, Jꢁ17.7, 8.9 Hz), 3.18 (1H,
(4-Methylphenyl)dodecane-1,12-diol 8c: Colorless crystals; mp 54.5— d, Jꢁ17.7, 2.8 Hz), 3.35 (1H, s, OH), 4.40—4.43 (1H, m), 7.48 (2H, t,
.
55.5 °C (AcOEt–hexane). IR (KBr) 3388 (OH), 2918, 2849, 1463, 1051 Jꢁ7.6 Hz), 7.59 (1H, t, Jꢁ7.6 Hz), 7.96 (2H, d, Jꢁ7.6 Hz). MS m/z (%) 164
1
cmꢀ1; H-NMR d 1.25—1.80 (20H, m), 2.34 (3H, s), 3.63 (2H, m), 4.64 (Mꢂ, 10), 146 (11), 120 (15), 105 (100), 77 (45), 51 (13). Calcd for
(1H, m), 7.16—7.24 (4H, m). MS m/z (%) 292 (Mꢂ, 6), 121 (6), 121 (100), C10H12O2: M, 164.0830. Found: m/z 164.0837.
93 (12), 77 (8). Calcd for C19H32O2: M, 292.2392. Found: m/z 292.2340.
Anal. Calcd: C, 78.03; H, 11.03. Found: C, 78.30; H, 11.10. 13-Phenyltride-
cane-1,12-diol 8d: Colorless crystals; mp 58—59 °C (AcOEt–hexane). IR
Acknowledgments This work was supported by a Grant-in-Aid for Sci-
entific Research from the Ministry of Education, Culture, Sports, Science
(KBr) 3373 (OH), 2920, 2850, 1084, 740, 697 cmꢀ1; 1H-NMR d 1.24—1.62 and Technology, Japan, which is gratefully acknowledged. We thank Ms.
(20H, m), 2.62—2.86 (2H, m) 3.62—3.65 (2H, m), 3.81 (1H, m), 7.21— Mayumi Kamiyama for her technical assistance.
7.52 (5H, m). MS m/z (%) 290 ([Mꢀ2H]ꢂ, 3), 201 (19), 109 (9), 92 (100),
91 (32), 55 (12). Anal. Calcd for C19H32O2: C, 78.03; H, 11.03. Found: C, References and Notes
77.95; H, 11.10. 1-Cyclohexyldodecane-1,12-diol 8e: Colorless oil; IR
1) Mijs W. J., de Jonge C. R. H. I., “Organic Synthesis by Oxidation with
Metal Compounds,” Plenum Press, New York, 1986.
2) Hudlicky M., “Oxidations in Organic Chemistry,” ACS Monograph
186, American Chemical Society, Washington, DC, 1990.
3) Jung M. E., Speltz L. M., J. Am. Chem. Soc., 98, 7882—7884 (1976).
4) Tomioka H., Takai K., Oshima K., Nozaki H., Tetrahedron Lett., 22,
1605—1608 (1981).
(neat) 3335 (OH), 2921, 2852, 1470, 1065 cmꢀ1 1H-NMR d 0.87—1.88
;
(30H, m), 3.33—3.37 (1H, m), 3.62—3.66 (2H, m). FAB-MS m/z 285
([MꢂH]ꢂ), 267, 201, 183, 137, 109, 97. Pentadec-13-ene-1,12-diol 8f: Col-
orless crystals; mp 72.5—73 °C (AcOEt–hexane). IR (KBr) 3366 (OH),
1
2917, 2850, 1462, 1055, 730 cmꢀ1; H-NMR d 1.27—1.72 (25H, m), 3.64
(2H, t, Jꢁ6.7 Hz), 4.46 (1H, dt, Jꢁ7.2, 6.7 Hz ), 5.37—5.50 (1H, m), 5.54—
5.69 (1H, m). MS m/z (%) 242 (Mꢂ, 4), 224 (6), 86 (11), 81 (9), 77 (100),
55 (14). Calcd for C15H30O2: M, 242.2236. Found: m/z 242.2244.
5) Tomioka H., Oshima K., Nozaki H., Tetrahedron Lett., 23, 539—542
(1982).
Ketoalcohols 9a—f 5-Hydroxy-1-phenyl-1-pentanone 9a: Colorless oil.
6) Stevens R. V., Chapman K. T., Stubbs C. A., Tam W. W., Albizai K. F.,
Tetrahedron Lett., 23, 4647—4650 (1982).
7) Kaneda K., Kawanishi Y., Jitsukawa K., Teranishi S., Tetrahedron
Lett., 24, 5009—5010 (1983).
8) Kanemoto S., Tomioka H., Oshima K., Nozaki H., Bull. Chem. Soc.
Jpn., 59, 105—108 (1986).
9) Miyata A., Murakami M., Irie R., Katsuki T., Tetrahedron Lett., 42,
7067—7070 (2001).
1
IR (neat) 3419 (OH), 2929, 1668 (CO), 1621, 1288, 1038 cmꢀ1; H-NMR d
0.68—1.28 (4H, m), 2.58—2.62 (2H, m), 3.85 (2H, t, Jꢁ6.3 Hz), 7.46—
7.95 (5H, m). FAB-MS m/z (%) 179 ([MꢂH]ꢂ), 177, 159, 148, 104, 68. 1-
(4-Chlorophenyl)-12-hydroxy-1-dodecanone 9b: Colorless oil. IR (neat)
3344 (OH), 2915, 2849, 1681 (CO), 1590, 1472, 1463, 1400, 1208, 1099,
1
1066 cmꢀ1; H-NMR d 1.25—1.35 (14H, m), 1.56 (2H, quintet, Jꢁ7.1 Hz),
1.72 (2H, quintet, Jꢁ7.1 Hz), 2.93 (2H, t, Jꢁ7.3 Hz), 3.64 (2H, t, Jꢁ
6.4 Hz), 7.43 (2H, d, Jꢁ7.3 Hz), 7.90 (2H, d, Jꢁ7.3 Hz). FAB-MS m/z 311 10) A review for selective oxidation of secondary alcohols; Arterburn J.
([MꢂH]ꢂ), 246, 185, 155, 154, 107, 95. Calcd for C18H28O2Cl: M,
B., Tetrahedron, 57, 9765—9788 (2001).
311.1781. Found: m/z 311.1772. 1-(4-Methylphenyl)-12-hydroxy-1-dode- 11) Miyata A., Furukawa M., Irie R., Katsuki T., Tetrahedron Lett., 43,
canone 9c: Colorless oil. IR (neat) 3430 (OH), 2915, 2849, 1682 (CO), 3481—3484 (2002).
1
1608, 1463, 1379, 1184, 1069, 813 cmꢀ1; H-NMR d 1.25—1.34 (14H, m), 12) Kanemoto S., Oshima K., Matsubara S., Takai K., Nozaki H., Tetrahe-
1.56 (2H, quintet, Jꢁ7.3 Hz), 1.72 (2H, quintet, Jꢁ7.3 Hz), 2.41 (3H, s),
2.93 (2H, t, Jꢁ7.3 Hz), 3.64 (2H, t, Jꢁ6.6 Hz), 7.25 (2H, d, Jꢁ8.3 Hz), 7.86
(2H, d, Jꢁ8.3 Hz). FAB-MS m/z 291 ([MꢂH]ꢂ), 289, 246, 185, 154, 137,
dron Lett., 24, 2185—2188 (1983).
13) Hayashi M., Kawabata H., J. Syn. Org. Chem. Jpn., 60, 137—144
(2002).
119, 93. Calcd for C19H31O2: M, 291.2318. Found: m/z 291.2340. 13-Hy- 14) Kim S. S., Kim D. W., Synlett, 2003, 1391—1394 (2003).
droxy-1-phenyltridecan-2-one 9d: Colorless oil. IR (neat) 3284 (OH), 2916,
15) Ayrey G., Barnard D., Woodbridge D. T., J. Chem. Soc., 1962, 2089—
2849, 1708 (CO), 1464, 1379, 1074 , 752, 699 cmꢀ1; 1H-NMR d 1.23—1.62
2099 (1962).
(18H, m), 2.43 (2H, m), 3.63—3.65 (2H, m), 3.68 (2H, s), 7.19—7.34 (5H, 16) BSA can be purchased from Aldrich.
m). FAB-MS m/z 291 ([MꢂH]ꢂ), 289, 246, 185, 154, 137, 119, 93. 1-Cyclo- 17) Barton D. H. R., Ley S. V., Magnus P. D., Rosenfeld M. N., J. Chem.

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Soc., Perkin Trans. I, 1977, 567—572 (1977).
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19) Barton D. H. R., Lester D. J., Ley S. V., J. Chem. Soc., Perkin Trans. I,
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21) Barton D. H. R., Brewster A. G., Hui R. A. H. F., Lester D. J., Ley S.
V., Chem. Commun., 1978, 952—954 (1978).
22) Yamakawa K., Satoh T., Ohba N., Sakaguchi R., Chem. Lett., 1979,
763—764 (1979).
23) Yamakawa K., Satoh T., Ohba N., Sakaguchi R., Takita S., Tamura N.,
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