B. F. Bonini, M. C. Franchini, M. Fochi, S. Mangini, G. Mazzanti, A. Ricci
FULL PAPER
(s, 3 H, CH3), 1.60Ϫ1.75 (m, 2 H, CH2), 1.85Ϫ2.20 (m, 2 H, CH2), as a colorless oil in 91%. Ϫ IR (CCl4): ν˜ ϭ 1720 cmϪ1 (CO). Ϫ 1H
2.50 (br. s, 1 H, OH), 2.58 (t, J ϭ 8.7 Hz, 2 H, CH2), 2.80Ϫ2.95 NMR (200 MHz, CDCl3): δ ϭ 1.42 (m, 2 H, CH2), 1.55 (m, 2 H,
(m, 1 H, iPr-CH), 5.75 (d, J ϭ 9.0 Hz, 1 H, vinylic H). Ϫ 13C NMR
CH2), 1.65 (m, 2 H, CH2), 2.11 (s, 3 H, CH3CO), 2.45 (t, J ϭ
(75.46 MHz, CDCl3): δ ϭ 22.7 (2ϫ CH3), 24.8 (CH2), 27.4 (CH3), 7.0 Hz, 2 H, CH2), 2.75 (t, J ϭ 7.2 Hz, 2 H, CH2), 6.20 (d, J ϭ
28.4 (CH), 30.8 (CH2), 41.4 (CH2), 70.7 (COH), 135.4 (vinylic CH),
11.0 Hz, 1 H, vinylic H), 6.45 (d, J ϭ 11.0 Hz, 1 H, vinylic H),
136.1 (vinylic C). Ϫ MS; m/z: 186 [Mϩ], 168 [Mϩ Ϫ H2O], 153 7.12Ϫ7.58 (m, 5 H, ArH). Ϫ 13C NMR (50.28 MHz, CDCl3): δ ϭ
[Mϩ Ϫ SH], 143 [Mϩ Ϫ CH(CH3)2], 43 [CH(CH3)2]. Ϫ HR-MS: 23.1, 27.8 (CH2), 29.7 (CH3), 29.8, 35.5, 43.3 (CH2), 125.3, 126.5,
C10H18OS calcd. 186.1078 found 186.1076.
127.4 128.1, 128.5 (3 ArCH ϩ 2 vinylic CH), 136.9 (ArC), 208.6
(CO). Ϫ MS; m/z: 248 [Mϩ], 149 [Mϩ Ϫ (CH2)4COCH3], 135 [Mϩ
Ϫ (CH2)5COCH3], 77 [C6H5], 43 [CH3CO]. Ϫ HR-MS: C15H20OS
calcd. 248.1235 found 248.1239.
2b: IR (CCl4): ν˜ ϭ 1720 cmϪ1 (CO). Ϫ 1H NMR (200 MHz,
CDCl3): δ ϭ 0.95 (d, J ϭ 6.5 Hz, 6 H, 2ϫ CH3), 1.79Ϫ1.91 (m, 2
H, CH2), 2.15 (s, 3 H, CH3), 2.58 (t, J ϭ 7.1 Hz, 2 H, CH2), 2.66
(t, J ϭ 7.0 Hz, 2 H, CH2), 2.60 (m, 1 H, iPr-CH), 5.42 (dd, J1 ϭ
J2 ϭ 9.2 Hz, 1 H, vinylic H), 5.76 (dd, J1 ϭ 9.3 Hz, J2 ϭ 0.8 Hz,
1 H, vinylic SCH). Ϫ 13C NMR (50.28 MHz, CDCl3): δ ϭ 22.2
(2ϫ CH3), 23.8 (CH2), 28.7 (CH), 30.0 (CH3), 33.1 (CH2), 41.6
(CH2), 122.0 (vinylic CH), 137.4 (vinylic CH), 208.0 (CO). Ϫ MS;
m/z: 188 [Mϩ], 117 [Mϩ Ϫ (CH2)2COCH3], 85 [(CH2)3COCH3],
71 [(CH2)2COCH3], 43 [CH(CH3)2]. Ϫ HR-MS: C10H18OS calcd.
186.1078 found 186.1072.
General Procedure for the Oxidation of Thietanols and Thiolanols
to the Corresponding Sulfones: To a solution of the cyclic sulfides
(3c, 7a, 3e) (1.0 mmol) in methanol (6 mL) cooled to 0 °C was
added a solution of oxone (3.0 mmol) in water (6 mL). The mix-
ture was allowed to warm to room temperature and after 5 h was
diluted with water and extracted with chloroform. The organic
layer was dried and concentrated under reduced pressure to give
the corresponding sulfone.
3-Hydroxy-3-methyl-2-[(Z)-phenylmethylidene]-1λ6-thietane-1,1-
dione (12): Yield 90% Ϫ m.p. 112Ϫ114 °C. Ϫ IR (CCl4): ν˜ ϭ 1110,
With procedure B, 1l gave 7a in 55% yield and 2b in 45% yield.
Following procedure C, 1m gave 7a in 70% yield and 2b in 15%
yield. Following method C, 1l was recovered unchanged.
1
1310 cmϪ1 (SO2). Ϫ H NMR (300 MHz, CDCl3): δ ϭ 1.75 (s, 3
H, CH3), 2.30 (br. s, 1 H, OH), 4.08 (dd, J1 ϭ J2 ϭ 13.7 Hz, 2 H,
CH2), 6.84 (s, 1 H, vinylic H), 7.41 (m, 3 H, ArH), 7.65 (m, 2 H,
ArH). Ϫ 13C NMR (75.46 MHz, CDCl3): δ ϭ 27.5 (CH3), 65.5
(CH2), 75.7 (COH), 129.2, 129.6, 131.0, 132.7, (3ϫ ArCH ϩ vinylic
CH), 131.2 (ArC), 156.0 (vinylic C). Ϫ MS; m/z: 224 [Mϩ], 207
[Mϩ Ϫ OH], 91 [C7H7]. Ϫ C11H12O3S (224.0507): calcd. C, 74.97
H, 6.87 S, 18.16 found C, 74.99 H, 6.83 S, 18.18.
3-Methyl-2-[(Z)-phenylmethylidene]tetrahydro-2H-thiopyran-3-ol
(7b): Following method B, 1n gave, after chromatography (light pet-
roleum/EtOAc, 5:1), 7b as the higher Rf fraction in 78% yield as a
colorless oil and, as the second Rf fraction, 2c in 22% yield as a
colorless oil. Ϫ 7b: IR (CCl4): ν˜ ϭ 3610 cmϪ1 bs (OH). Ϫ 1H NMR
(200 MHz, CDCl3): δ ϭ 1.65 (s, 3 H, CH3), 1.75Ϫ1.90 (m, 2 H,
CH2), 2.01Ϫ2.25 (m, 2 H, CH2), 2.40 (br. s, 1 H, OH), 2.62Ϫ2.73
(m, 2 H, CH2) 7.11 (s, 1 H, vinylic H), 7.20Ϫ7.60 (m, 5 H, ArH).
4-Hydroxy-4-methyl-5-[(Z)-phenylmethylidene]dihydro-1H-1λ6-thio-
phene-1,1(2H)-dione (13): Yield 70% Ϫ m.p. 115Ϫ117 °C Ϫ IR
(CCl4): ν˜ ϭ 1130, 1300 cmϪ1 (SO2), 3590 (OH). Ϫ 1H NMR
(300 MHz, CDCl3): δ ϭ 1.65 (s, 3 H, CH3), 2.31 (m, 3 H, OH ϩ
CH2), 3.12 (m, 1 H, HaCH2), 3.40 (m, 1 H, HbCH2), 7.05 (s, 1 H,
vinylic H), 7.40 (m, 3 H, ArH), 7.60 (m, 2 H, ArH). Ϫ 13C NMR
(75.46 MHz, CDCl3): δ ϭ 28.2 (CH3), 35.2, 49.6 (CH2), 75.2
(COH), 128.6, 130.2, 130.4, 134.1, (3ϫ ArCH ϩ vinylic CH), 131.7
(ArC), 144.0 (vinylic C). Ϫ MS; m/z: 238 [Mϩ], 223 [Mϩ Ϫ CH3],
146 [Mϩ Ϫ C2H4SO2], 91 [C7H7]. Ϫ C12H14O3S (238.0664): calcd.
C, 75.76 H, 7.42 S, 16.82 found C, 75.72 H, 7.44 S, 16.84.
Ϫ
13C NMR (50.28 MHz, CDCl3): δ ϭ 24.9 (CH2), 28.3 (CH3),
30.8, 41.5 (CH2), 71.9 (C), 126.1, 127.1 127.8, 129.6 (3 ArCH ϩ
vinylic CH), 136.4, 140.4 (ArC ϩ vinylic C). Ϫ MS; m/z: 220 [Mϩ],
202 [Mϩ Ϫ H2O], 134 [Mϩ Ϫ CH3CH2CH2COCH3]. Ϫ HR-MS:
C13H16OS calcd. 220.0922 found 220.0925.
2c: IR (CCl4): ν˜ ϭ 1730 cmϪ1 (CO). Ϫ 1H NMR (200 MHz,
CDCl3): δ ϭ 1.96 (m, 2 H, CH2), 2.15 (s, 3 H, CH3), 2.61 (t, J ϭ
7.0 Hz, 2 H, CH2CO), 2.82 (t, J ϭ 6.9 Hz, 2 H, CH2S), 6.21(d, J ϭ
11.0 Hz, 1 H, vinylic H), 6.47 (d, J ϭ 11.0 Hz, 1 H, vinylic SCH),
7.15Ϫ7.51 (m, 5 H, ArH). Ϫ 13C NMR (50.28 MHz, CDCl3): δ ϭ
23.8 (CH2), 30.0 (CH3), 35.0, 41.5 (CH2), 126.0, 126.7, 126.9, 128.2,
128.6, (3 ArCH ϩ 2 vinylic CH), 136.9 (ArC), 207.6 (CO). Ϫ MS;
m/z: 220 [Mϩ], 135 [Mϩ Ϫ (CH2)3COCH3], 85 [(CH2)3COCH3], 43
[COCH3]. Ϫ HR-MS: C13H16OS calcd. 220.0922 found 220.0920.
Following the procedure C, 1n gave 7b in 76% yield and 2c in
20% yield.
(3R)-3-[(1S)-1-(Dibenzylamino)ethyl]-3-hydroxy-2-[(Z)-phenylmeth-
ylidene]-1λ6-thietane-1,1-dione (14): Yield 85% Ϫ Colorless solid Ϫ
Ϫ1
˜
m.p. 121Ϫ124 °C Ϫ IR (CCl4): ν ϭ 1150, 1300 cm (SO2), 3480
1
(OH). Ϫ H NMR (300 MHz, CDCl3): δ ϭ 1.34 (d, J ϭ 6.9 Hz, 3
H, CH3), 3.05 (q, J ϭ 6.9 Hz, 1 H, CH), 3.33 (d, J ϭ 13.7 Hz, 2
H, 2ϫ HaϪCH2Ph), 4.03 (m, 4 H, 2ϫ HbϪCH2Ph ϩ CH2S), 4.20
(br. s, 1 H, OH), 6.82 (s, 1 H, vinylic H), 7.22Ϫ7.40 (m, 13 H,
ArH), 7.53 (m, 2 H, ArH). Ϫ 13C NMR (75.46 MHz, CDCl3): δ ϭ
6.6 (CH3), 55.5 (CH2), 59.6 (CH), 71.3 (COH), 72.6 (CH), 127.4,
128.6, 128.9, 129.5, 130.7, 134.2, 138.8 (6ϫ ArCH ϩ vinylic CH),
6-[(Z)-2-Phenylvinyl]sulfanyl-2-hexanone (2d): Following procedure
B, 1o gave, after chromatography (light petroleum/EtOAc, 5:1), 2d
as a colorless oil in 53% yield. Ϫ IR (CCl4): ν˜ ϭ 1720 cmϪ1 (CO).
Ϫ 1H NMR (300 MHz, CDCl3): δ ϭ 1.66Ϫ1.74 (m, 4 H, 2ϫ CH2),
2.13 (s, 3 H, CH3), 2.42Ϫ2.50 (m, 2 H, CH2), 2.74Ϫ2.83 (m, 2 H,
CH2), 6.21 (d, J ϭ 11.0 Hz, 1 H, vinylic H), 6.42 (d, J ϭ 11.0 Hz,
1 H, vinylic H), 7.1Ϫ7.5 (m, 5 H, ArH). Ϫ 13C NMR (75.46 MHz,
CDCl3): δ ϭ 22.5, 29.6 (CH2), 29.7 (CH3), 35.5, 43.0 (CH2), 125.5,
126.6, 127.2, 128.1, 128.5 (3 ArCH ϩ 2 vinylic CH), 134.0, 137.2
(C), 208.1 (CO). Ϫ MS; m/z: 234 [Mϩ], 135 [Mϩ Ϫ (CH2)4COCH3],
99 [(CH2)4COCH3], 77 [C6H5], 71 [(CH2)2COCH3]. Ϫ HR-MS:
C14H18OS calcd. 234.1078 found 234.1075.
131.4 (ArC), 154.9 (vinylic C). Ϫ MS; m/z: 433 [Mϩ], 353 [Mϩ
Ϫ
SO3], 91 [C7H7]. Ϫ C26H27NO3S (433.1712): calcd. C, 81.00 H, 7.06
N, 3.64 S, 8.30 found C, 80.89 H, 7.10 N, 3.60 S, 8.41. Suitable
crystals for X-ray diffraction analysis were grown from diethyl ether
Ϫ pentane: the product crystallized as colorless thin needles.
3-Methyl-2-[(Z)-phenylmethylidene]-3-thietanyl Acetate (15): To a
solution of 3c (0.15 g, 0.78 mmol) in pyridine (2 mL) were added
4-(dimethylamino)pyridine (DMAP) (0.19 g, 1.56 mmol) and acetic
anhydride (0.15 mL, 1.56 mmol). After 12 h the mixture was di-
luted with diethyl ether, the organic layer was separated and washed
with aqueous HCl (1 ) and 10% NaHCO3 solution, then dried
7-[(Z)-2-Phenylvinyl]sulfanyl-2-heptanone (2e): Following method
B, 1p gave, after chromatography (light petroleum/EtOAc, 5:1), 2e
2398
Eur. J. Org. Chem. 2000, 2391Ϫ2399