L. F. Frey et al. / Tetrahedron 59 (2003) 6363–6373
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completion. Aqueous HCl was used to remove the TBS
group. Yield of 1,3-thiazol-5-yl[2-(trifluoromethyl)phenyl]-
methanone was 84%. H NMR (CDCl3) d 9.11 (s, 1H),
calcd for C16H13F6NO4S (Mþ) m/z 430.0548, found m/z
430.0554.
1
8.02 (s, 1H), 7.83 (m, 1H), 7.69 (m, 2H), 7.55 (m, 1H); 13C
NMR (CDCl3) d 186.9, 160.5, 150.6, 139.8, 137.1 (q,
J¼1.7 Hz), 131.7, 130.7, 128.1 (q, J¼32.4 Hz), 128.0,
127.0 (q, J¼4.7 Hz), 123.4 (q, J¼274.2 Hz); HR-MS
calcd for C11H6F3NOS (Mþ) m/z 258.0201, found m/z
258.0186.
Product Table 3, entry 9: Following the general procedure
given above the reaction was aged for 7 h to reach
completion. Yield of (3,4-dimethoxyphenyl){2-[2,2,2-tri-
fluoro-1-(methoxymethoxy)-1-(trifluoromethyl)ethyl]-1,3-
thiazol-5-yl}methanone was 94%. 1H NMR (CDCl3) d 8.34
(s, 1H), 7.60 (dd, J¼2.0, 8.4 Hz, 1H), 7.49 (d, J¼1.9 Hz,
1H), 6.98 (d, J¼8.4 Hz, 1H), 5.17 (s, 2H), 4.00 (s, 3H), 3.98
(s, 3H), 3.59 (s, 3H); 13C NMR (CDCl3) d 185.0, 163.7,
154.0, 149.5, 147.1, 142.2, 129.6, 124.4, 121.3 (q,
J¼291.9 Hz, 2C), 111.4, 110.2, 95.3, 80.3 (m), 57.2, 56.2,
56.1; Anal. Calcd for C17H15F6NO5S: C 44.45; H 3.29; N
3.05. Found C 44.17 H 3.00 N 3.02.
Product Table 3, entry 4: Following the general procedure
given above the reaction was aged for 3 h to reach
completion. Yield of {2-[tert-butyl(dimethyl)silyl]-1,3-thia-
1
zol-5-yl}(3-methoxyphenyl)methanone was 90%. H NMR
(CDCl3) d 8.53 (s, 1H), 7.45 (m, 3H), 7.17 (m, 1H), 3.88 (s,
3H), 1.01 (s, 9H), 0.44 (s, 6H); 13C NMR (CDCl3) d 187.1,
181.4, 159.8, 150.8, 141.0, 139.3, 129.6, 121.8, 119.4,
113.5, 55.5, 26.2, 16.9, 25.5; HR-MS calcd for C17H23-
NO2SSi (Mþ) m/z 334.1297, found m/z 334.1314.
Product Table 3, entry 10: Following the general procedure
given above the reaction was aged for 20 min to reach
completion. Yield of [2-(methylthio)-1,3-thiazol-5-yl](pyri-
din-4-yl)methanone was 96%. 1H NMR (DMSO-d6) d 8.81
(dd, J¼1.6, 4.4, 2H), 8.29 (s, 1H), 7.74 (dd, J¼1.6, 4.4, 2H),
2.79 (s, 3H); 13C NMR (DMSO-d6) d 185.4, 177.9, 151.2,
151.0, 143.9, 137.5, 122.5, 16.9: Anal. Calcd for
C10H8N2OS2: C 50.82; H 3.41; N 11.85. Found C 50.78;
H 3.11; N 11.72.
Product Table 3, entry 5: Following the general procedure
given above the reaction was aged for 3 h to reach
completion. Aqueous HCl was used to remove the TBS
group. Yield of (3-methoxyphenyl)(1,3-thiazol-5-yl)metha-
1
none was 87%. H NMR (CDCl3) d 8.59 (s, 1H), 8.40 (s,
1H), 7.47 (m, 3H), 7.19 (m, 1H), 3.89 (s, 3H); 13C NMR
(CDCl3) d 186.9, 159.9, 159.2, 149.1, 139.3, 138.8, 129.8,
121.7, 119.5, 113.7, 55.5; HR-MS calcd for C11H9NO2S
(Mþ) m/z 220.0432, found m/z 220.0425.
Product Table 3, entry 11: Following the general procedure
given above, the reaction was aged for 20 min to reach
completion to obtain {2-[tert-butyl(dimethyl)silyl]-1,3-thia-
1
zol-5-yl}(pyridin-4-yl)methanone in 90% yield: H NMR
Product Table 3, entry 6: Following the general procedure
given above the reaction was aged for 12 h to reach
completion. Aqueous HCl was used to remove the TBS
group. Yield of (3,4-dimethoxyphenyl)(1,3-thiazol-5-
(DMSO-d6) d 8.83 (dd, J¼1.7, 4.3, 2H), 8.67 (s, 1H), 7.77
(dd, J¼1.7, 4.3, 2H), 0.95 (s, 9H), 0.40 (s, 6H); 13C NMR
(DMSO-d6) d 186.4, 182.2, 152.4, 151.0, 144.4, 140.4,
122.6, 26.5, 17.0, 25.2.
1
yl)methanone was 91%. H NMR (CDCl3) d 9.05 (s, 1H),
8.39 (s, 1H), 7.59 (dd, J¼2.0, 8.4 Hz, 1H), 7.49 (d,
J¼2.0 Hz, 1H), 6.97 (d, J¼8.4 Hz, 1H), 3.99 (s, 3H), 3.97
(s, 3H); 13C NMR (CDCl3) d 185.6, 158.5, 153.7, 149.4,
148.2, 139.3, 130.3, 124.2, 111.6, 110.3, 56.2, 56.1; Anal.
Calcd for C12H11NO3S: C 57.82; H 4.45; N 5.62. Found C
57.44 H 4.26 N 5.53.
Product Table 3, entry 12: Following the general procedure
given above the reaction was aged for 8 h to reach
completion. Aqueous HCl was used to remove the TBS
group. Yield of 2-furyl(1,3-thiazol-5-yl)methanone was
1
60%. H NMR (CDCl3) d 9.06 (s, 1H), 8.91 (s, 1H), 7.74
(dd, J¼0.6, 1.5 Hz, 1H), 7.47 (d, J¼3.6 Hz, 1H), 6.67 (dd,
J¼1.7, 3.6 Hz, 1H); 13C NMR (CDCl3) d 172.7, 158.9,
152.1, 148.5, 147.0, 138.0, 119.4, 112.9; HR-MS calcd for
C8H5NO2S (Mþ) m/z 180.0119, found m/z 180.0114.
Product Table 3, entry 7: Following the general procedure
given above the reaction was aged for 3 h to reach
completion. Yield of phenyl{2-[2,2,2-trifluoro-1-(methoxy-
methoxy)-1-(trifluoromethyl)ethyl]-1,3-thiazol-5-yl}-
methanone was 95%. 1H NMR (CDCl3) d 8.34 (s, 1H), 7.92
(d, J¼7.6 Hz, 2H), 7.69 (t, J¼7.2 Hz, 1H), 7.57 (t,
J¼7.5 Hz, 2H), 5.17 (s, 2H), 3.59 (s, 3H); 13C NMR
(CDCl3) d 186.7, 164.3, 148.0, 142.1, 136.9, 133.5, 129.2,
128.9, 121.3 (q, J¼290.9 Hz, 2C), 95.4, 80.7 (m), 57.1;
Anal. Calcd for C16H15F6NO3S: C 45.12; H 2.78; N 3.51.
Found C 44.99 H 2.59 N 3.47.
1
Product with TBS: H NMR (CDCl3) d 9.00 (s, 1H), 7.72
(dd, J¼0.7, 1.6, 1H), 7.45 (dd, J¼0.7, 3.6, 1H), 6.65 (dd,
J¼1.6, 3.6, 1H), 1.01 (s, 9H), 0.44 (s, 6H); 13C NMR
(CDCl3) d 181.0, 172.8, 152.2, 150.2, 146.8, 139.6, 119.2,
112.8, 26.2, 16.9, 25.5.
Product Table 3, entry 13: Following the general procedure
given above the reaction was aged for 30 h to reach
completion. Yield of cyclopropyl[2-(2-methyl-1,3-dioxo-
lan-2-yl)-1,3-thiazol-5-yl]methanone was 47%. 1H NMR
(CDCl3) d 8.40 (s, 1H), 4.10 (m, 4H), 2.49 (m, 1H), 1.84 (s,
3H), 1.28 (m, 2H), 1.08 (m, 2H); 13C NMR (CDCl3) d 192.8,
178.8, 146.8, 141.0, 106.9, 65.6, 25.1, 18.9, 11.8; Anal.
Calcd for C11H13NO3S: C 55.21; H 5.48; N 5.85. Found C
54.90 H 5.30 N 5.83.
Product Table 3, entry 8: Following the general procedure
given above the reaction was aged for 5 h to reach
completion. Yield of (4-methoxyphenyl){2-[2,2,2-trifluoro-
1-(methoxymethoxy)-1-(trifluoromethyl)ethyl]-1,3-thiazol-
5-yl}methanone was 96%. 1H NMR (CDCl3) d 8.32 (s, 1H),
7.95 (dd, J¼2.0, 6.8 Hz, 2H), 7.03 (dd, J¼2.0, 6.9 Hz, 2H),
5.16 (s, 2H), 3.93 (s, 3H), 3.59 (s, 3H); 13C NMR (CDCl3) d
185.0, 164.1, 163.7, 147.1, 142.3, 131.8, 129.5, 121.3 (q,
J¼291.1 Hz, 2C), 114.2, 95.3, 80.7 (m), 57.2, 55.6; HR-MS
Product Table 3, entry 14: Following the general procedure
given above the reaction was aged for 7.5 h to reach