P. Hoyos et al. / Tetrahedron 67 (2011) 7321e7329
7325
2H, J¼8.22 Hz). 13C NMR (63 MHz, CDCl3):
d
23.8, 25.1, 32.1, 33.8,
C19H22O2S2: C, 65.86; H, 6.40; S, 18.51. Found: C, 65.40; H, 6.18; S,
18.22. 1H NMR (250 MHz, CDCl3):
51.2, 126.7, 127.6, 136.3, 149.1.
d
1.30 (t, 3H, J¼7.03 Hz),1.77e1.89
(m, 2H), 2.50e2.69 (m, 4H), 3.90 (q, 2H, J¼7.03 Hz), 4.88 (s, 1H),
4.2.3. Synthesis of 2-(4-chlorophenyl)-1,3-dithiane (4c). White solid
(1.095 g, 95% yield). Anal. Calcd for C10H11ClS2: C, 52.04; H, 4.80; S,
27.79. Found: C, 51.95; H, 4.78; S, 27.70. 1H NMR (250 MHz, CDCl3):
6.55e6.72 (m, 4H), 7.21e7.27 (m, 3H), 7.57e7.64 (m, 2H). 13C NMR
(63 MHz, CDCl3): d 14.7, 24.7, 26.9, 27.2, 63.2, 66.5, 80.6, 112.9, 127.1,
128.1, 129.1, 129.2, 130.5, 137.3, 158.7.
d
1.75e1.93 (m, 1H), 2.05e2.19 (m, 1H), 2.79e3.06 (m, 4H), 5.05 (s,
41H), 7.21e7.27 (m, 2H), 7.31e7.38 (m, 2H). 13C NMR (63 MHz,
CDCl3): 24.9, 31.9, 50.5, 128.9, 129.1, 134.1, 137.6.
4.2.10. Synthesis of (4-chlorophenyl)(2-phenyl-1,3-dithian-2-yl)
methanol [(R,S)-5e]. White solid (621 mg, 87% yield). Anal. Calcd
for C17H17ClOS2: C, 60.61; H, 5.09; S, 19.04. Found: C, 59.65; H,
d
4.2.4. Synthesis of 2-(3,4-dichlorophenyl)-1,3-dithiane (4d). White
solid (1.260 g, 95% yield). Anal. Calcd for C10H10Cl2S2: C, 45.29; H,
3.80; S, 24.18. Found: C, 45.22; H, 3.81; S, 24.15. 1H NMR (250 MHz,
4.75; S, 18.52. 1H NMR (250 MHz, CDCl3):
d 1.5 (s, 1H), 1.77e1.96
(m, 2H), 2.50e2.73 (m, 4H), 4.88 (s, 1H), 6.68e6.74 (m, 2H),
6.99e7.05 (m, 2H), 7.19e7.29 (m, 3H), 7.56e7.63 (m, 2H). 13C NMR
CDCl3):
d
1.84e2.04 (m, 1H), 2.12e2.28 (m, 1H), 2.87e3.16 (m, 4H),
(63 MHz, CDCl3):
129.4, 130.3.
d 24.6, 26.8, 27.2, 75.6, 89.0, 127.1, 127.7, 128.3,
5.12 (s, 1H), 7.31e7.37 (m, 1H), 7.41e7.46 (m, 1H), 7.61 (d, 1H,
J¼2.11 Hz). 13C NMR (63 MHz, CDCl3):
d 24.8, 31.8, 49.9, 127.2, 129.9,
130.6, 132.4, 132.7, 139.2.
4.2.11. Synthesis of (2-(4-chlorophenyl)-1,3-dithian-2-yl)(phenyl)
methanol [(R,S)-5f]. White solid (644 mg, 90% yield). Anal. Calcd for
C17H17ClOS2: C, 60.61; H, 5.09; S, 19.04. Found: C, 59.80; H, 4.83; S,
4.2.5. Synthesis of 2-(thiophen-2-yl)-1,3-dithiane (4e). White solid
(930 mg, 92% yield). Anal. Calcd for C8H10S3: C, 47.48; H, 4.98; S,
47.54. Found: C, 47.30; H, 4.96; S, 47.45. 1H NMR (250 MHz, CDCl3):
18.76. 1H NMR (250 MHz, CDCl3):
d 1.51 (s, 1H), 1.80e1.90 (m, 2H),
2.44e2.72 (m, 4H), 4.92 (s, 1H), 6.77e6.83 (m, 2H), 7.04e7.21 (m,
d
1.79e1.99 (m, 1H), 2.05e2.13 (m, 1H), 2.78e3.00 (m, 4H), 5.33 (s,
5H), 7.53 (d, 2H, J¼8.97 Hz). 13C NMR (63 MHz, CDCl3):
d 24.6, 26.9,
1H), 6.89 (dd, 1H, J¼3.59, 5.16 Hz), 7.09 (dd, 1H, J¼1.30, 3.59 Hz),
27.1, 65.7, 80.9, 127.1, 128.1, 128.3, 132.2, 133.5, 135.9, 136.9.
7.20 (dd, 1H, J¼1.30, 5.16 Hz). 13C NMR (63 MHz, CDCl3):
d 24.9, 30.9,
44.6, 125.6, 126.2, 126.7, 142.5.
4.2.12. Synthesis of (3,4-dichlorophenyl)(2-phenyl-1,3-dithian-2-yl)
methanol [(R,S)-5g]. White solid (684 mg, 87% yield). Anal. Calcd for
C17H16Cl2OS2: C, 54.98; H, 4.34; S, 17.27. Found: C, 54.38; H, 4.10; S,
4.2.6. Synthesis of (2-(4-ethoxyphenyl)-1,3-dithian-2-yl)(phenyl)
methanol [(R,S)-5d]9. Compound 4a (510 mg, 2.12 mmol) was dis-
solved in 5 mL of anhydrous THF and n-BuLi (1.39 mL, 2.22 mmol)
was added drop wise. The mixture was stirred at ꢂ78 ꢀC under
16.89. 1H NMR (250 MHz, CDCl3):
d 1.60 (s, 1H), 1.89e2.03 (m, 2H),
2.62e2.83 (m, 4H), 4.94 (s, 1H), 6.69 (dd, 1H, J¼2.04, 8.32 Hz), 6.92
(d, 1H, J¼2.04 Hz), 7.20 (d, 1H, J¼8.32 Hz), 7.31e7.39 (m, 3H),
argon during 1 h and then benzaldehyde (280
mL, 2.75 mmol) was
7.65e7.72 (m, 2H). 13C NMR (63 MHz, CDCl3):
d 24.5, 26.8, 27.2, 66.1,
added. The reaction was left to warm to room temperature and
stirred for 5 h. The reaction was quenched by the addition of NH4Cl
0.5 M (5 mL) and the organic phase was collected and dried over
Na2SO4. The solution was filtered and the solvent evaporated. The
product was purified by column chromatography (SiO2, CH2Cl2), to
afford (R,S)-5d as a white solid (550 mg. 1.59 mmol, 75% yield).
Anal. Calcd for C19H22O2S2: C, 65.86; H, 6.40; S, 18.51. Found: C,
79.7, 127.4, 127.9, 128.4, 128.7, 130.1, 131.1, 136.9, 137.3.
4.2.13. Synthesis of (2-(3,4-dichlorophenyl)-1,3-dithian-2-yl)(phenyl)
methanol [(R,S)-5h]. White solid (660 mg, 84% yield). Anal. Calcd
for C17H16Cl2OS2: C, 54.98; H, 4.34; S, 17.27. Found: C, 54.25; H, 4.05;
S, 16.85. 1H NMR (250 MHz, CDCl3):
d 1.69 (s, 1H), 1.88e2.11 (m, 2H),
2.59e2.85 (m, 4H), 5.01 (s, 1H), 6.88e6.95 (m, 2H), 7,16e7.27 (m,
3H), 7.34e7.39 (m, 1H), 7.51 (dd, 1H, J¼2.31, 8.56 Hz), 7.81 (d, 1H,
65.00; H, 6.05; S, 18.15. 1H NMR (250 MHz, CDCl3):
d 1.31 (t, 3H,
J¼7.02 Hz), 1.74e1.73 (m, 2H), 2.52e2.64 (m, 4H), 3.92 (c, 2H,
J¼7.02 Hz), 4.85 (s, 1H), 6.68 (d, 2H, J¼8.89 Hz), 6.76 (d, 2H,
J¼9.08 Hz), 6.98e7.11 (m, 3H), 7.43 (d, 2H, J¼8.89 Hz). 13C NMR
J¼2.31 Hz). 13C NMR (63 MHz, CDCl3):
d 24.4, 26.9, 27.1, 65.1, 77.1,
127.2, 128.1, 128.5, 129.7, 130.3, 132.8.
(63 MHz, CDCl3):
d
15.2, 25.2, 27.3, 27.6, 63.8, 66.4, 81.5, 114.2, 126.3,
4.2.14. Synthesis of (4-(methylthio)phenyl)(2-phenyl-1,3-dithian-2-
yl)methanol [(R,S)-5i]. White solid (628 mg, 85% yield). Anal.
Calcd for C18H20OS3: C, 62.03; H, 5.78; S, 27.60. Found: C, 61.65; H,
127.4, 128.4, 128.6, 128.8, 129.2, 132.3, 137.7, 158.7.
4.2.7. Synthesis of (4-isopropylphenyl)(2-phenyl-1,3-dithian-2-yl)
methanol [(R,S)-5a]. White solid (621 mg, 85% yield). Anal. Calcd for
C20H24OS2: C, 69.72; H, 7.02; S, 18.61. Found: C, 69.26; H, 6.25; S,
5.25; S, 27.15. 1H NMR (250 MHz, CDCl3):
d 1.68e1.78 (m, 2H), 2.23
(s, 3H), 2.23e2.60 (m, 4H), 4.76 (s, 1H), 6.57 (d, 2H, J¼8.2 Hz), 6.82
(d, 2H, J¼8.2 Hz), 7.08e7.16 (m, 3H), 7.46e7.52 (m, 2H). 13C NMR
18.12. 1H NMR (250 MHz, CDCl3):
d
1.22(d, 6H, J¼6.87 Hz),1.88e2.00
(63 MHz, CDCl3): d 15.5, 24.7, 26.9, 27.2, 66.4, 80.6, 124.8, 127.6,
(m, 2H), 2.65e2.76 (m, 4H), 2.78e2.92 (m, 1H), 5.00 (s, 1H), 6.82 (d,
2H, J¼7.82 Hz), 7.03 (d, 2H, J¼7.82 Hz), 7.30e7.38 (m, 3H), 7.68e7.78
128.2, 128.5, 130.5, 133.9, 137.2, 138.3.
(m, 2H). 13C NMR (63 MHz, CDCl3):
d
24.3, 25.3, 27.5, 27.8, 34.3, 66.9,
4.2.15. Synthesis of (2-methoxyphenyl)(2-phenyl-1,3-dithian-2-yl)
methanol [(R,S)-5j]. White solid (640 mg, 90% yield). Anal. Calcd for
C18H20O2S2: C, 65.02; H, 6.06; S, 19.29. Found: C, 64.54; H, 5.65; S,
81.5, 125.6, 127.8, 128.5, 129.0, 131.1, 135.0, 137.9, 149.4.
4.2.8. Synthesis of (2-(4-isopropylphenyl)-1,3-dithian-2-yl)(phenyl)
methanol [(R,S)-5b]. White solid (657 mg, 90% yield). Anal. Calcd for
C20H24OS2: C, 69.72; H, 7.02; S, 18.61. Found: C, 69.05; H, 6.10; S,
18.90. 1H NMR (250 MHz, CDCl3):
d 1.86e2.04 (m, 2H), 2.52e2.85
(m, 4H), 3.29 (s, 3H), 5.32 (s, 1H), 6.65 (d, 1H, J¼8.29 Hz), 6.84e6.90
(m, 1H), 7.09e7.13 (m, 1H), 7.19e7.34 (m, 4H), 7.74e7.78 (m, 2H). 13C
18.32. 1H NMR (250 MHz, CDCl3):
d
1.18 (d, 6H, J¼6.85 Hz),
NMR (63 MHz, CDCl3): d 24.8, 26.9, 27.2, 54.7, 66.7, 78.6,109.9,119.5,
127.0, 127.8, 129.1, 130.2, 130.7, 137.6, 157.1.
1.80e1.89 (m, 2H), 2.56e2.67 (m, 4H), 2.84 (h, 1H, J¼6.85 Hz), 4.88
(s, 1H), 6.77e6.84 (m, 2H), 6.95e7.15 (m, 5H), 7.50 (d, 2H,
J¼8.92 Hz). 13C NMR (63 MHz, CDCl3):
d
23.9, 24.0, 24.8, 26.9, 27.2,
4.2.16. Synthesis of (4-isopropylphenyl)(2-(thiophen-2-yl)-1,3-
dithian-2-yl)methanol [(R,S)-5k]. White solid (608 mg, 82% yield).
Anal. Calcd for C18H22OS3: C, 61.67; H, 6.33; S, 27.44. Found: C,
33.5, 77.1, 81.0, 126.2, 126.9, 127.5, 128.0, 128.1, 128.6, 130.3, 134.5,
137.3, 148.3.
60.95; H, 5.94; S, 26.87. 1H NMR (250 MHz, CDCl3):
d 1.13 (d, 6H,
4.2.9. Synthesis
of
(4-ethoxyphenyl)(2-phenyl-1,3-dithian-2-yl)
J¼6.93 Hz), 1.74e1.97 (m, 2H), 2.65e3.06 (m, 5H), 4.90 (s, 1H),
methanol [(R,S)-5c]. White solid (683 mg, 93% yield). Anal. Calcd for
6.84e6.90 (m, 4H), 7.24 (dd, 1H, J¼1.58, 0.73 Hz). 13C NMR (63 MHz,