A new synthesis of 2-sulfanyl allylic alcohols and α-sulfanyl ketones from carbonyl compounds and 1-chloroalkyl p-tolyl sulfoxides with carbon-carbon bond-formation

Article abstract of DOI:10.1248/cpb.54.1734

Reaction of lithium α-sulfinyl carbanions of 1-chloroalkyl p-tolyl sulfoxides with ketones or aldehydes at low temperature gave adducts in almost quantitative yields. Treatment of the adducts derived from ketones with trifluoroacetic anhydride (TFAA) in t

Full text of DOI:10.1248/cpb.54.1734

1734
Notes
Chem. Pharm. Bull. 54(12) 1734—1738 (2006)
Vol. 54, No. 12
a
A New Synthesis of 2-Sulfanyl Allylic Alcohols and -Sulfanyl Ketones
from Carbonyl Compounds and 1-Chloroalkyl p-Tolyl Sulfoxides with
Carbon–Carbon Bond-Formation
Tsuyoshi SATOH,* Yoshinori TAKAHASHI, Yuuichi SHIRAI, and Yukie YAMADA
Department of Chemistry, Faculty of Science, Tokyo University of Science; Ichigaya-Funagawara-machi, Shinjuku-ku,
Tokyo 162–0826, Japan. Received July 21, 2006; accepted September 6, 2006
Reaction of lithium a-sulfinyl carbanions of 1-chloroalkyl p-tolyl sulfoxides with ketones or aldehydes at low
temperature gave adducts in almost quantitative yields. Treatment of the adducts derived from ketones with tri-
fluoroacetic anhydride (TFAA) in the presence of NaI in acetone gave a-sulfanyl allylic alcohols in good to quan-
titative yields. On the other hand, treatment of the adducts derived from aldehydes with TFAA and NaI resulted
in the formation of a-sulfanyl ketones and/or a-sulfanyl allylic alcohols. These reactions offer a good method for
the synthesis of the above-mentioned compounds from ketones and aldehydes with carbon–carbon bond-forma-
tion in two steps and in good yields.
Key words sulfoxide; Pummerer reaction; 2-sulfanyl allylic alcohol; a-sulfanyl ketone
Organosulfur compounds are very valuable in organic syn- high to quantitative yields. On the other hand, the adducts de-
thesis and innumerable studies for their chemistry and appli- rived from aldehydes (3, R2ꢀH) were treated with TFAA-
cations in organic synthesis have been reported.1—6) Espe- NaI to give a-sulfanylated ketones 5 and/or the allylic alco-
cially, sulfoxides have a variety of reactivity and are most ex- hols 4, depending on the substituents on the adducts 3, in
tensively used in organic synthesis.7—9) We also have long good to high yields. These products, 4 and 5, are quite im-
been interested in the organosulfur compounds in organic portant compounds in organic synthesis. Details of this pro-
synthesis. We recently focused our attention on 1-chloroalkyl cedure and the reaction mechanisms are discussed.
aryl sulfoxides as useful compounds in organic synthesis,
A representative example of the reaction is described as
many novel synthetic methods of which have appeared.10—20) follows (Chart 2). Thus, treatment of 1-chloroalkyl p-tolyl
In continuation of our interest in the use of 1-chloroalkyl aryl sulfoxide 2a13) with slight excess of LDA in THF at ꢁ78 °C
sulfoxides in organic synthesis, we recently treated the a- resulted in the formation of lithium a-sulfinyl carbanion. To
chloro-b-hydroxy sulfoxides, which were synthesized from this reaction mixture was added cyclohexanone to afford the
carbonyl compounds and 1-chloroalkyl p-tolyl sulfoxide, adduct 3a in 91% yield as a single product. The adduct 3a
with trifluoroacetic anhydride (TFAA) in the presence of NaI, was next treated with excess TFAA in the presence of NaI in
and quite interesting results were obtained (Chart 1).
acetone at 0 °C for 10 min.21,22) A quite clean reaction took
Thus, addition reaction of lithium a-sulfinyl carbanion of place and the product was found to have a hydroxyl group
1-chloroalkyl p-tolyl sulfoxides 2 to carbonyl compounds 1 and one vinylic hydrogen and the structure was found to be
gave adducts, b-hydroxy sulfoxides 3, in high to quantitative the allylic alcohol having a sulfanyl group 4a.
yields. The adducts 3 were treated with TFAA and NaI in
Obviously, this reaction was recognized to be a very inter-
acetone at 0 °C to give 2-sulfanylated allylic alcohols 4 in esting method for synthesis of allylic alcohols having a sul-
Chart 1
Chart 2
∗ To whom correspondence should be addressed. e-mail: tsatoh@rs.kagu.tus.ac.jp
© 2006 Pharmaceutical Society of Japan

December 2006
1735
Table 1. Treatment of the a-Chloro b-Hydroxy Sulfoxides 3 Derived from Ketones with TFAA in the Presence of NaI in Acetone at 0 °C
3
4
Entry
R1
R2
R3
R4
Yield/%
1
2
3b
3c
H
4b
4c
97a)
97b)
Ph
Ph
H
H
H
3
4
3d
3e
CH3
CH3
4d
4e
97c)
92d)
–(CH2)5–
H
5
6
3f
H
H
H
H
4f
96
96
3g
CH3CH2CH2
CH3CH2CH2
4g
7
8
3h
3i
Ph
Ph
H
H
4h
4i
99
97
97
85
CH3
CH3
H
H
9
3j
–(CH2)14–
H
H
4j
10
3k
CH3
CH3
CH3
CH3
4k
11
12
3l
CH3
CH3
CH3
CH3
4l
85
95
3m
–(CH2)5–
4m
a) E : Zꢀ8 : 2. b) E : Zꢀ5 : 4. c) E : Zꢀ7 : 1. d) The reaction was conducted at ꢁ50 °C.
fanyl group at the b-position from two components, 1-
chloroalkyl p-tolyl sulfoxides and ketones, with carbon–car-
bon bond-formation in only two steps. We first examined the
generality of these reactions and the results are summarized
in Table 1.
Cyclohexane-1,4-dione mono ethylene ketal, benzophe-
none, acetone, cyclohexanone, 4-heptanone, and cyclopen-
tadecanone were used as the representative examples of the
ketones. 1-Chloro-4-(4-methoxyphenyl)butyl p-tolyl sulfox-
ide, 1-chloroethyl p-tolyl sulfoxide, and 1-chloro-2-methyl-
propyl p-tolyl sulfoxide were used as the sulfoxides. The ad-
dition reaction of the 1-chloroalkyl p-tolyl sulfoxides to ke-
Chart 3
tones took place without any problem to give the adducts 3 in however, only a reduced product,24) b-hydroxy sulfide 7, was
almost quantitative yields. obtained in quantitative yield (Chart 3). On the other hand,
All the reactions of 3 were carried out with 5 eq of TFAA treatment of the b-hydroxy sulfoxide having a chlorine atom
in the presence of NaI (5 eq) in acetone at 0 °C for 10 min. 3e with TFAA without NaI resulted in the formation of a
The reaction of the adducts 3b—d gave the allylic alcohols complex mixture. From these results, the chlorine atom and
4b—d as a mixture of two geometrical isomers (entries 1— NaI are proved to be essential for this reaction.
3). E-Isomers were obtained as main products and the ratio
We next investigated the above-mentioned reaction with
of the configurational isomers was found to be variable with the a-chloro b-hydroxysulfoxides derived from aldehydes
the substrates.23) All the other adducts (3e—m) gave the al- and the results are summarized in Table 2.
lylic alcohols (4e—m) in high to quantitative yields (entries
First, 2-chloro-2-(p-tolylsulfinyl)-1-phenyl-1-propanol 3n
5—12). From these results, we are sure this reaction is of was synthesized from 1-chloroethyl p-tolyl sulfoxide and
value for the synthesis of allylic alcohol having a sulfanyl benzaldehyde in quantitative yield as a mixture of two di-
group at the b-position 4 from ketones in short steps and in astereomers. The sulfoxide 3n was treated with TFAA-NaI in
high yield.
acetone at 0 °C for 10 min. Somewhat surprisingly, the main
At this stage of the investigation, we thought that it should product was a-sulfanyl ketone 5n (49%) with a trace amount
be better to clarify the necessity of the chlorine atom in the of the expected allylic alcohol 4n (entry 1). The reaction was
sulfoxide and NaI as the reagent. We synthesized b-hydroxy conducted at 25 and 40 °C (entries 2, 3), and total yield of 4n
sulfoxide 6 and treated it with TFAA in the presence of NaI; and 5n was found to be variable with the reaction tempera-

1736
Vol. 54, No. 12
Table 2. Synthesis of 2-Sulfanyl Allylic Alcohols 4 and a-Sulfanyl Ketones 5 from 1-Chloroethyl p-Tolyl Sulfoxide 2 and Aldehydes through the a-
Chloro b-Hydroxy Sulfoxides 3
3
Temperature
°C
4
5
Entry
R1
Yield/%
Yield/%
1
2
3
4
5
6
7
3n
Ph
0
25
40
0
40
0
4n
Trace
5n
49
40
71
50
54
58
75
23
26
0
0
0
3o
3p
PhCH2
4o
4p
5o
5p
PhCH2CH2
40
0
derived from aldehydes, competitive deprotonation of the hy-
drogen on the carbon bearing R3 and R4, and the hydrogen on
the carbon bearing the hydroxyl group takes place. In the lat-
ter case, the product is an enolate C and tautomerism gives
the a-sulfanyl ketone 5.
Experimental
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, diisopropylamine was distilled from CaH2 and THF was
distilled from diphenylketyl and acetone was dried over CaSO4 and distilled
before use.
1-[1-Chloro-4-(4-methoxyphenyl)-1-(p-tolylsulfinyl)butyl]cyclohexanol
(3a) To a solution of LDA (11.8 mmol) in THF (50 ml) at ꢁ78 °C was
added dropwise with stirring a solution of 2a (3.32 g, 9.86 mmol) in 5 ml of
THF and the solution was stirred for 15 min. Cyclohexanone (1.27 ml,
12.3 mmol) was added to the reaction mixture and the stirring was continued
for 15 min. The reaction was quenched with sat. aq. NH4Cl, and the whole
was extracted with CH2Cl2. The organic layer was washed with water and
dried over MgSO4. The solvent was evaporated and the residue was purified
by silica gel column chromatography to give 3a (3.90 g, 91%) as colorless
crystals; mp 105—106 °C (AcOEt–hexane); IR (KBr) 3307 (OH), 2931,
1511, 1241, 1030 (SO), 829, 814, 512 cmꢁ1 1H-NMR d 1.07—1.19 (1H,
;
m), 1.20—1.32 (1H, m), 1.43—1.50 (1H, m), 1.54—1.88 (10H, m), 1.86—
2.00 (2H, m), 2.18—2.23 (1H, m), 2.35—2.42 (1H, m), 2.43 (3H, s), 3.80
(3H, s), 6.80 (2H, d, Jꢀ8.3 Hz), 6.93 (2H, d, Jꢀ8.3 Hz ), 7.26 (2H, d,
Jꢀ7.0 Hz), 7.52 (2H, d, Jꢀ7.0 Hz); Anal. Calcd for C24H32ClO3S: C, 66.26;
H, 7.18; Cl, 8.15; S, 7.37. Found: C, 66.29; H, 7.12; Cl, 8.04; S, 7.70.
Other adducts 3b—q were synthesized in the same manner described
above.
Chart 4
ture. As shown in entry 3, a-sulfanyl ketone 5n was obtained
in 71% yield as a main product. a-Sulfanyl ketones also are
quite interesting and important compounds in organic syn-
thesis.25)
We finally investigated the generality of this reaction and
the results are summarized in Table 2. The adducts derived
from 1-chloroethyl p-tolyl sulfoxide and phenylacetaldehyde
and 3-phenylpropanal (3o, 3p) gave a-sulfanyl ketones 5o
and 5p in up to 75% yield without the allylic alcohol 4 (en-
tries 4—7).
1-[4-(4-Methoxyphenyl)-1-(p-tolylsulfanyl)-1-butenyl]cyclohexanol
(4a) To a solution of 3a (48 mg, 0.11 mmol) in acetone (5 ml) in a flame-
dried flask was added NaI (84 mg, 0.56 mmol) and (CF3CO)2O (0.56 mmol)
at 0 °C under argon atmosphere. After 5 min, the reaction was quenched
with sat. aq. Na2SO3 and sat. aq. NaHCO3, and the whole was extracted with
CH2Cl2. The organic solution was washed with water and dried over anhy-
drous MgSO4. The solvent was evaporated and the residue was purified by
silica gel column chromatography to give 4a (42.4 mg, 99%) (E/Zꢀ8 : 1). E-
4a; colorless oil. IR (neat) 3564 (OH), 2927, 1513, 1245, 1033, 807 cmꢁ1
;
1H-NMR d 1.08—1.15 (1H, m), 1.46—1.64 (8H, m), 1.80 (2H, dt, Jꢀ14.1,
4.0 Hz), 2.32 (3H, s), 2.61 (2H, t, Jꢀ7.4 Hz), 2.75 (2H, q, Jꢀ7.6 Hz), 3.78
(3H, s), 5.72 (1H, t, Jꢀ7.6 Hz), 6.81 (2H, d, Jꢀ8.5 Hz), 7.04 (2H, d,
Jꢀ8.5 Hz), 7.06 (2H, d, Jꢀ7.3 Hz), 7.16 (2H, d, Jꢀ7.3 Hz); MS m/z (%) 382
(Mꢂ, 57), 261 (31), 243 (27), 149 (29), 137 (67), 121 (100), 119 (17), 91
(19). Calcd for C24H30O2S: M, 382.1966. Found: m/z 382.1959. Z-4a; color-
less oil. IR (neat) 3480 (OH), 2929, 1513, 1247, 1037, 805 cmꢁ1; 1H-NMR d
The mechanism of this reaction is presumed to be the
Pummerer-type reaction26—28) as shown in Chart 4. At first,
the reaction of the sulfoxide 3 with TFAA gives an acyloxy-
sulfonium ion A. The iodide anion then attacks the chlorine
atom in A to afford thionium ion B. Deprotonation from the
thionium ion takes place to give the allylic alcohol having a
sulfanyl group 4. When this reaction was carried out with 3 1.15—1.21 (1H, m), 1.48—1.73 (9H, m), 2.00 (1H, s, OH), 2.27 (3H, s),

December 2006
1737
150 (49), 149 (47), 135 (100), 105 (28), 91 (24), 77 (8), 59 (49). Calcd for
C12H16OS: M, 208.0921. Found: m/z 208.0921.
2.48—2.61 (4H, m), 3.77 (3H, s), 6.39 (1H, t, Jꢀ6.7 Hz), 6.77 (2H, d,
Jꢀ8.9 Hz), 6.99 (2H, d, Jꢀ8.9 Hz), 7.01 (2H, d, Jꢀ8.0 Hz), 7.07 (2H, d,
Jꢀ8.0 Hz); MS m/z (%) 382 (Mꢂ, 53), 261 (27), 243 (29), 149 (27), 137
(56), 121 (100), 119 (19), 91 (19). Calcd for C24H30O2S: M, 382.1966.
Found: m/z 382.1971.
4j: Colorless oil. IR (neat) 3296 (OH), 2927, 2854, 1491, 1458, 808 cmꢁ1
;
1H-NMR d 1.32—1.38 (26H, m), 1.63—1.69 (2H, m), 1.80—1.86 (2H, m),
1.93 (1H, s, OH), 2.35 (3H, s), 4.67 (1H, d, Jꢀ0.9 Hz), 5.26 (1H, d,
Jꢀ0.9 Hz), 7.16 (2H, d, Jꢀ7.9 Hz), 7.36 (2H, d, Jꢀ7.9 Hz); MS m/z (%) 374
(Mꢂ, 100), 251 (7), 225 (4), 150 (35), 124 (12), 105 (10), 91 (7). Calcd for
C24H38OS: M, 374.2643. Found: m/z 374.2659.
The Allylic Alcohols 4b—m in Table 1 4b: E-4b; colorless oil. IR
1
(neat) 3481 (OH), 2929, 1615, 1515, 1246, 1104, 1036, 965, 808 cmꢁ1; H-
NMR d 1.52—1.63 (4H, m), 1.91 (2H, dt, Jꢀ13.5, 4.0 Hz), 2.16 (2H, dt,
Jꢀ13.5, 4.0 Hz), 2.32 (3H, s), 2.62 (2H, t, Jꢀ7.3 Hz), 2.73 (2H, q,
Jꢀ7.6 Hz), 3.79 (3H, s), 3.93 (4H, t, Jꢀ2.8 Hz), 5.77 (1H, t, Jꢀ8.0 Hz),
6.18 (2H, d, Jꢀ8.3 Hz), 7.07 (4H, d, Jꢀ8.9 Hz), 7.16 (2H, d, Jꢀ8.0 Hz); MS
m/z (%) 440 (Mꢂ, 46), 319 (28), 301 (11), 195 (69), 151 (16), 121 (100), 99
(23). Calcd for C26H32O4S: M, 440.2022. Found: m/z 440.2026. Z-4b; color-
4k: Colorless oil. IR (neat) 3400 (OH), 2928, 1599, 1490, 1366, 1119,
1
804 cmꢁ1; H-NMR d 1.49 (6H, s), 2.04 (3H, s), 2.15 (3H, s), 2.28 (3H, s),
2.53 (1H, s, OH), 7.05 (4H, s). MS m/z (%) 236 (Mꢂ, 96), 218 (21), 203
(14), 178 (100), 163 (58), 143 (32), 133 (33), 105 (21), 91 (30). Calcd for
C14H20OS: M, 236.1234. Found: m/z 236.1234.
less oil. IR (neat) 3480 (OH), 2928, 1514, 1247, 1096, 1036, 980, 806 cmꢁ1
;
4l: Colorless oil. IR (neat) 3468 (OH), 2928, 1596, 1491, 1375, 1099,
1
1035, 805, 768 cmꢁ1; H-NMR d 1.54—1.60 (2H, m), 1.67—1.71 (2H, m),
1H-NMR d 1.57—1.78 (4H, m), 1.89—2.01 (4H, m), 2.10 (1H, s), 2.27 (3H,
s), 2.50—2.60 (4H, m), 3.77 (3H, s), 3.91—3.97 (4H, m), 6.40 (1H, t,
Jꢀ7.0 Hz), 6.78 (2H, d, Jꢀ8.3 Hz), 7.00 (4H, t, Jꢀ8.3 Hz), 7.06 (4H, d,
Jꢀ8.3 Hz); MS m/z (%) 440 (Mꢂ, 26), 319 (22), 301 (11), 257 (7), 239 (4),
195 (42), 151 (14), 121 (100), 99 (24), 91 (13). Calcd for C26H32O4S: M,
440.2021. Found: m/z 440.2021.
1.97 (2H, dt, Jꢀ13.2, 4.3 Hz), 2.05 (3H, s), 2.19 (3H, s), 2.28 (3H, s), 2.32
(2H, dt, Jꢀ13.2, 4.3 Hz), 2.33 (1H, s, OH), 3.93 (4H, t, Jꢀ2.1 Hz), 7.04
(4H, s). MS m/z (%) 334 (Mꢂ, 52), 316 (29), 178 (100), 163 (28), 149 (27),
124 (20), 101 (73), 91 (32). Calcd for C19H26O3S: M, 334.1601. Found: m/z
334.1611.
4m: Colorless oil. IR (neat) 3468 (OH), 2927, 2856, 1491, 1447, 1258,
4c: E-4c; colorless oil. IR (neat) 3504 (OH), 2925, 1511, 1247, 805,
1
1084, 803 cmꢁ1; H-NMR d 1.50—1.53 (2H, m), 1.56—1.66 (4H, m), 1.71
1
701 cmꢁ1; H-NMR d 2.29 (3H, s), 2.24—2.51 (4H, m), 3.67 (1H, s, OH),
(2H, d, Jꢀ12.5 Hz), 1.90—1.97 (3H, m), 2.03 (3H, s), 2.21 (3H, s), 2.28
(3H, s), 7.03 (4H, s). MS m/z (%) 276 (Mꢂ, 51), 258 (33), 178 (100), 163
(27), 143 (12), 133 (16), 107 (20), 91 (31). Calcd for C17H24OS: M,
276.1546. Found: m/z 276.1544.
3.80 (3H, s), 5.63 (1H, t, Jꢀ7.1 Hz), 6.79 (2H, d, Jꢀ8.5 Hz), 6.91 (2H, d,
Jꢀ8.5 Hz), 7.04 (2H, d, Jꢀ8.0 Hz), 7.16 (2H, d, Jꢀ8.0 Hz), 7.20—7.22 (4H,
m), 7.24—7.31 (8H, m); MS m/z (%) 466 (Mꢂ, 38), 284 (41), 221 (24), 191
(32), 163 (37), 121 (100), 105 (63), 77 (21). Calcd for C31H30O2S: M,
466.1964. Found: m/z 466.1968. Z-4c; colorless oil. IR (neat) 3472 (OH),
Allylic Alcohol 4n and a-Sulfanyl Ketones 5n, 5o, and 5p in Table 2
4n: Colorless oil. IR (neat) 3419 (OH), 1679, 1448, 1233, 1019, 950,
1
3023, 2922, 1612, 1514, 1447, 1246, 1178, 1035, 809, 762, 701 cmꢁ1; H-
1
799 cmꢁ1; H-NMR d 2.34 (3H, s), 5.04 (1H, s), 5.27 (1H, s), 5.51 (1H, s),
NMR d 1.72 (2H, q, Jꢀ7.4 Hz), 2.26 (2H, t, Jꢀ7.7 Hz), 2.33 (3H, s), 3.54
(1H, s, OH), 3.77 (3H, s), 5.95 (1H, t, Jꢀ7.6 Hz), 6.72 (4H, s), 7.07 (2H, d,
Jꢀ8.3 Hz), 7.22 (2H, d, Jꢀ8.3 Hz), 7.26—7.30 (10H, m); MS m/z (%) 466
(Mꢂ, 24), 448 (6), 284 (24), 221 (43), 187 (27), 163 (30), 121 (100), 105
(64). Calcd for C31H30O2S: M, 466.1964. Found: m/z 466.1962.
7.13 (2H, d, Jꢀ7.9 Hz), 7.30—7.32 (3H, m), 7.34—7.37 (2H, m), 7.41 (2H,
d, Jꢀ7.9 Hz). MS m/z (%) 256 (Mꢂ, 100), 246 (7), 150 (37), 149 (53), 135
(61), 115 (15), 105 (63), 91 (30). Calcd for C16H16OS: M, 256.0920. Found:
m/z 256.0918.
5n30): Colorless oil. IR (neat) 2926, 1681 (CO), 1448, 1233, 1178, 950,
4d: E-4d; colorless oil. IR (neat) 3401 (OH), 2982, 2940, 1513, 1247,
1
812, 718 cmꢁ1; H-NMR d 1.50 (3H, d, Jꢀ6.8 Hz), 2.31 (3H, s), 4.55 (1H,
1036, 732 cmꢁ1 1H-NMR d 1.38 (6H, s), 1.95 (1H, s, OH), 2.32 (3H, s),
;
q, Jꢀ6.8 Hz), 7.07 (2H, d, Jꢀ8.0 Hz), 7.21—7.24 (2H, m), 7.43 (2H, t,
Jꢀ7.6 Hz), 7.54 (1H, m), 7.95 (2H, m) . MS m/z (%) 256 (Mꢂ, 33), 151
(100), 123 (25), 105 (29), 91 (8), 77 (27). Calcd for C16H16OS: M, 256.0920.
Found: m/z 256.0912.
2.60—2.73 (4H, m), 3.79 (3H, s), 5.72 (1H, t, Jꢀ7.5 Hz), 6.82 (2H, d,
Jꢀ8.5 Hz), 7.05 (2H, d, Jꢀ8.5 Hz), 7.08 (2H, d, Jꢀ8.0 Hz), 7.18 (2H, d,
Jꢀ8.0 Hz); MS m/z (%) 342 (Mꢂ, 51), 221 (48), 203 (22), 149 (37), 121
(100), 97 (79), 91 (16). Calcd for C21H26O2S: M, 342.1652. Found: m/z
342.1656. Z-4d; colorless oil. IR (neat) 3448 (OH), 2923, 1511, 1246, 1037,
5o: Colorless oil. IR (neat) 2924, 1713 (CO), 1493, 1454, 1375, 1032,
809 cmꢁ1 1H-NMR d 1.33 (3H, d, Jꢀ7.0 Hz), 2.32 (3H, s), 3.76 (1H, q,
;
805 cmꢁ1 1H-NMR d 1.39 (6H, s), 2.28 (3H, s), 2.52 (2H, t, Jꢀ7.1 Hz),
;
Jꢀ7.0 Hz), 3.88 (1H, d, Jꢀ15.3 Hz), 3.95 (1H, d, Jꢀ15.3 Hz), 7.09 (2H, d,
Jꢀ7.9 Hz), 7.17 (2H, d, Jꢀ7.0 Hz), 7.23—7.25 (3H, m), 7.30 (2H, t,
Jꢀ7.9 Hz). MS m/z (%) 270 (Mꢂ, 22), 151 (100), 147 (12), 123 (17), 91
(36). Calcd for C17H18OS: M, 270.1078. Found: m/z 270.1083.
5p: Colorless oil. IR (neat) 3027, 2926, 1709 (CO), 1493, 1454, 811,
699 cmꢁ1; 1H-NMR d 1.32 (3H, d, Jꢀ7.2 Hz), 2.32 (3H, s), 2.83—2.89 (3H,
m), 3.01—3.06 (1H, m), 3.63 (1H, q, Jꢀ7.2 Hz), 7.07 (2H, d, Jꢀ8.4 Hz),
7.16—7.21 (5H, m), 7.27 (2H, t, Jꢀ7.2 Hz). MS m/z (%) 284 (Mꢂ, 34), 151
(100), 123 (13), 105 (10), 91 (19). Calcd for C18H20OS: M, 284.1235.
Found: m/z 284.1230.
2.59 (2H, t, Jꢀ7.1 Hz), 3.77 (3H, s), 6.40 (1H, t, Jꢀ6.7 Hz), 6.79 (2H, d,
Jꢀ8.6 Hz), 7.00 (2H, d, Jꢀ8.6 Hz), 7.02 (2H, d, Jꢀ8.2 Hz), 7.07 (2H, d,
Jꢀ8.2 Hz); MS m/z (%): 342 (Mꢂ, 54), 221 (50), 203 (23), 149 (37), 121
(100), 97 (68), 91 (14). Calcd for C21H26O2S: M, 342.1652. Found: m/z
342.1652.
4e: Colorless crystals; mp 94—95 °C (AcOEt–hexane); IR (KBr) 3335
(OH), 2925, 2854, 1599, 1447, 1121, 979, 873, 813 cmꢁ1 1H-NMR d
;
1.20—1.29 (1H, m), 1.56—1.84 (9H, m), 2.35 (3H, s), 4.67 (1H, s), 5.41
(1H, s), 7.15 (2H, d, Jꢀ8.0 Hz), 7.36 (2H, d, Jꢀ8.0 Hz); MS m/z (%) 248
(Mꢂ, 100), 150 (72), 149 (27), 135 (65), 99 (35), 81 (41). Calcd for
C15H20OS: M, 248.1235. Found: m/z 248.1235. Anal. Calcd: C, 72.53; H,
8.12; S, 12.91. Found: C, 72.67; H, 8.26; S, 12.99.
References and Notes
1) Block E., “Reactions of Organosulfur Compounds,” Academic Press,
New York, 1978.
2) Simpkins N. S., “Sulphones in Organic Synthesis,” Academic Press,
New York, 1993.
3) Metzner P., Thuillier A., “Sulfur Reagents in Organic Synthesis,” Aca-
demic Press, Lonson, 1994.
4) Page P. (ed.), “Organosulfur Chemistry, Synthetic Aspects,” Academic
Press, Lonson, 1995.
4f: Colorless crystals; mp 81—83 °C (AcOEt–hexane). IR (KBr) 3445
(OH), 2961, 1489, 1096, 950, 811 cmꢁ1 1H-NMR d 1.64—1.67 (2H, m),
;
1.83 (1H, s, OH), 1.84—1.87 (2H, m), 1.98—2.05 (2H, m), 2.07—2.13 (2H,
m), 2.34 (3H, s), 3.93—3.99 (4H, m), 4.72 (1H, s), 5.44 (1H, s) 7.16 (2H, d,
Jꢀ7.9 Hz), 7.35 (2H, d, Jꢀ7.9 Hz); MS m/z (%) 306 (Mꢂ, 97), 278 (23), 150
(30), 135 (26), 105 (26), 99 (100), 91 (19). Calcd for C17H22O3S: M,
306.1289. Found: m/z 306.1289.
1
4g: Colorless oil. IR (neat) 3483 (OH), 2959, 1492, 1105, 810 cmꢁ1; H-
5) Whitham G. H., “Organosulfur Chemistry,” Oxford University Press,
Oxford, 1995.
6) Page P. (ed.), “Organosulfur Chemistry, Synthetic and Stereochemical
Aspects,” Academic Press, Lonson, 1998.
7) Patai S., Rappoport Z., Stirling C. (ed.), “The Chemistry of Sulphones
and Sulphoxides,” John Wiley and Sons, Chicester, 1988.
8) Patai S., Rappoport Z. (ed.), “The Syntheses of Sulphones, Sulphox-
ides and Cyclic Sulphides,” John Wiley and Sons, Chichester, 1994.
9) Mikolajczk M., Drabowicz J., Kielbasinski P., “Chiral Sulfur Reagents,
Applications in Asymmetric and Stereoselective Synthesis,” CRC
Press, Boca Raton, 1997.
NMR d 0.94 (6H, t, Jꢀ7.4 Hz), 1.33—1.42 (4H, m), 1.60—1.66 (2H, m),
1.73—1.79 (2H, m), 2.36 (3H, s), 4.54 (1H, s), 5.23 (1H, s), 7.17 (2H, d,
Jꢀ8.0 Hz), 7.37 (2H, d, Jꢀ8.0 Hz); MS m/z (%): 264 (Mꢂ, 25), 222 (100),
193 (15), 151 (51), 150 (43), 135 (51), 71 (46). Calcd for C16H24OS: M,
264.1546. Found: m/z 264.1547.
4h: Colorless oil. IR (neat) 3505 (OH), 3025, 1491, 1447, 1019, 759,
701 cmꢁ1; 1H-NMR d 2.31 (3H, s), 3.49 (1H, s, OH), 4.98 (1H, s), 5.12 (1H,
s), 7.12 (2H, d, Jꢀ7.9 Hz), 7.19—7.37 (8H, m), 7.43—7.45 (4H, m); MS
m/z (%) 332 (Mꢂ, 35), 191 (15), 183 (77), 150 (100), 135 (18), 105 (77), 77
(39). Calcd for C22H20OS: M, 332.1235. Found: m/z 332.1236.
4i29): Colorless oil. IR (neat) 3401 (OH), 2978, 1492, 1364, 1104,
1
810 cmꢁ1; H-NMR d 1.51 (6H, s), 2.35 (3H, s), 4.61 (1H, s), 5.37 (1H, s),
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11) Satoh T., Fukuda, Y., Tetrahedron, 59, 9803—9810 (2003).
7.16 (2H, d, Jꢀ8.0 Hz), 7.36 (2H, d, Jꢀ8.0 Hz); MS m/z (%) 208 (Mꢂ, 87),

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Vol. 54, No. 12
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