D. Be´rard et al. / Tetrahedron 64 (2008) 7537–7544
7543
HMRS (ESI): calcd for C15H21O2 (MHþ): 233.1536; found: 233.1531.
Compound 43: 1H (300 MHz, CDCl3)
J¼8.2 Hz), 4.90 (m, 1H), 3.26 (dd, 1H, J¼15.4, 8.2 Hz), 2.82 (dd, 1H,
J¼15.4, 8.2 Hz), 1.26 (mþs, 4H), 1.05 (dd, 1H, J¼14.3, 8.8 Hz), 0.09 (s,
d¼7.83 (d, 1H, J¼8.2 Hz), 7.71
(d, 2H, J¼8.8 Hz), 7.52 (t, 1H, J¼7.6 Hz), 7.34 (t, 1H, J¼7.6 Hz), 7.12 (d,
1H, J¼8.8 Hz), 6.51 (d, 1H, J¼5.5 Hz), 4.34 (t, 1H, J¼7.1 Hz), 4.12 (t,
1H, J¼8.2 Hz), 3.64 (m, 1H), 2.41 (m, 1H), 2.30 (m, 1H). 13C (75 MHz,
9H). 13C (75 MHz, CDCl3)
d
¼158.0, 129.4, 127.6, 124.8, 118.4, 110.0,
82.9, 38.1, 25.1, ꢀ0.8. HMRS (ESI): calcd for C12H18OClSi (MHþ):
241.0810; found: 241.0811. Compound 52c: 1H (300 MHz, CDCl3)
CDCl3)
d
¼156.7, 130.1, 129.7, 129.6, 129.0, 126.9, 123.0, 122.0, 118.3,
d
¼7.23 (d, 1H, J¼1.7 Hz), 7.18 (dd, 1H, J¼8.2, 1.7 Hz), 6.60 (d, 1H,
111.8, 111.6, 67.4, 45.9, 31.8. HMRS (ESI): calcd for C14H13O2 (MHþ):
J¼8.2 Hz), 4.93 (m, 1H), 3.27 (dd, 1H, J¼15.4, 8.2 Hz), 2.79 (dd, 1H,
J¼15.4, 8.2 Hz), 1.30 (dd, 1H, J¼14.3, 6.6 Hz), 1.09 (dd, 1H, J¼14.3,
213.0910; found: 213.0912. NMR data of dihydropyrans. Compound
40a: 1H (300 MHz, CDCl3)
d
¼7.17 (dþs, 2H, J¼8.2 Hz), 6.79 (d, 1H,
8.8 Hz), 0.09 (s, 9H). 13C (75 MHz, CDCl3)
d
¼158.0, 129.4, 127.6,
J¼8.2 Hz), 5.87 (d, 1H, J¼6.6 Hz), 3.85–3.65 (m, 2H), 3.29 (dd, 1H,
124.8, 118.4, 110.0, 82.9, 38.1, 25.1, ꢀ0.8. HMRS (ESI): calcd for
12H18OBrSi (MHþ): 285.0305; found: 285.0313. Compound 52d:
1H (300 MHz, CDCl3)
J¼11.5, 5.5 Hz), 2.05 (m, 1H), 1.92 (m, 1H), 1.60 (m, 2H), 1.31 (s, 9H).
C
13C (75 MHz, CDCl3)
d
¼156.0, 144.0, 128.9, 124.9, 120.6, 108.8, 104.2,
d¼7.41 (d, 1H, J¼1.7 Hz), 7.36 (dd, 1H, J¼8.2,
61.1, 38.9, 34.3, 31.7, 22.8, 20.1. HMRS (ESI): calcd for C15H21O2
1.7 Hz), 6.51 (d, 1H, J¼8.2 Hz), 4.92 (m, 1H), 3.26 (dd, 1H, J¼15.4,
8.2 Hz), 2.77 (dd, 1H, J¼15.4, 8.2 Hz), 1.29 (dd, 1H, J¼14.3, 6.6 Hz),
1.07 (dd, 1H, J¼14.3, 8.8 Hz), 0.08 (s, 9H). 13C (75 MHz, CDCl3)
(MHþ): 233.1536; found: 233.1542. Compound 40b: 1H (300 MHz,
CDCl3)
1H, J¼6.6 Hz), 3.81–3.62 (m, 2H), 3.27 (dd, 1H, J¼11.5, 5.5 Hz), 2.01
(m, 1H), 1.83 (m, 1H), 1.54 (m, 2H). 13C (75 MHz, CDCl3)
d¼7.08 (dþs, 2H, J¼8.2 Hz), 6.74 (d, 1H, J¼8.2 Hz), 5.86 (d,
d
¼159.3, 136.6, 133.5, 130.4, 111.5, 82.8, 37.8, 25.1, ꢀ0.9. HMRS (ESI):
d¼156.9,
calcd for C12H18OISi (MHþ): 333.0166; found: 333.0162. Compound
129.4, 128.1, 125.7, 124.0, 110.7, 104.5, 61.0, 38.8, 22.5, 19.8. HMRS
52e: 1H (300 MHz, CDCl3)
d¼6.71 (s, 1H), 6.62 (d, 1H, J¼8.2 Hz), 6.58
(ESI): calcd for C11H12O2Cl (MHþ): 211.0520; found: 211.0511.
(d, 1H, J¼8.2 Hz), 4.85 (m, 1H), 3.71 (s, 3H), 3.21 (dd, 1H, J¼15.4,
8.2 Hz), 2.74 (dd, 1H, J¼15.4, 8.2 Hz), 1.28 (dd, 1H, J¼14.3, 6.6 Hz),
1.07 (dd, 1H, J¼14.3, 8.8 Hz), 0.07 (s, 9H). 13C (75 MHz, CDCl3)
Compound 40c: 1H (300 MHz, CDCl3)
d
¼7.26 (dþs, 2H, J¼8.2 Hz),
6.74 (d, 1H, J¼8.2 Hz), 5.89 (d, 1H, J¼6.6 Hz), 3.83–3.65 (m, 2H), 3.31
(dd, 1H, J¼11.5, 5.5 Hz), 2.04 (m, 1H), 1.87 (m, 1H), 1.60 (m, 2H). 13
C
d
¼153.7, 128.3, 113.1, 112.5, 111.3, 108.9, 82.3, 56.0, 38.6, 25.1, ꢀ0.8.
(75 MHz, CDCl3)
d
¼157.4, 131.9, 131.0, 126.9, 112.8, 111.3, 104.5, 61.0,
HMRS (ESI): calcd for C13H21O2Si (MHþ): 237.1305; found: 237.1296.
38.7, 22.5, 19.8. HMRS (ESI): calcd for C11H10O2Br (MHþ): 255.0015;
Compound 52f: 1H (300 MHz, CDCl3)
d¼7.01 (d, 1H, J¼1.7 Hz), 6.94
found: 255.0011. Compound 40d: 1H (300 MHz, CDCl3)
d
¼7.28 (d,
(dd, 1H, J¼8.2, 1.7 Hz), 6.67 (d, 1H, J¼8.2 Hz), 4.91 (m, 1H), 3.81 (t,
2H, J¼6.4 Hz), 3.26 (dd, 1H, J¼15.4, 8.2 Hz), 2.79 (m, 3H), 1.33 (dd,
1H, J¼14.3, 6.6 Hz), 1.09 (dd, 1H, J¼14.3, 8.8 Hz), 0.10 (s, 9H). 13C
1H, J¼8.2 Hz), 6.79 (d, 1H, J¼8.8 Hz), 5.89 (d, 1H, J¼6.6 Hz), 3.83–
3.64 (m, 2H), 3.31 (dd, 1H, J¼11.5, 5.5 Hz), 2.05 (m, 1H), 1.86 (m, 1H),
1.60 (m, 2H), 1.31 (s, 9H). 13C (75 MHz, CDCl3)
d¼159.1, 133.6, 131.9,
(75 MHz, CDCl3)
d¼158.1, 129.7, 128.3, 127.8, 125.4, 109.0, 82.3, 63.9,
129.2, 128.5, 109.3, 104.2, 61.0, 38.5, 22.7, 20.0, ꢀ0.7. HMRS (ESI):
38.5, 38.2, 25.2, ꢀ0.8. HMRS (ESI): calcd for C14H23O2Si (MHþ):
calcd for C14H21O2Si (MHþ): 249.1305; found: 249.1310. Compound
251.1462; found: 251.1463. Compound 52g: 1H (300 MHz, CDCl3)
40e: 1H (300 MHz, CDCl3)
d
¼7.55 (d, 2H, J¼8.2 Hz), 7.48–7.37 (m,
d
¼7.68 (d, 2H, J¼8.2 Hz), 7.29 (d, 2H, J¼8.2 Hz), 6.85 (d, 1H,
4H), 7.32 (t, 1H, J¼7.2 Hz), 6.94 (d, 1H, J¼8.2 Hz), 5.96 (d, 1H,
J¼6.6 Hz), 3.89–3.69 (m, 2H), 3.39 (dd, 1H, J¼11.5, 6.0 Hz), 2.10 (m,
J¼1.7 Hz), 6.76 (dd,1H, J¼8.2,1.7 Hz), 6.60 (d,1H, J¼8.2 Hz), 4.89 (m,
1H), 4.40 (t, 1H, J¼6.6 Hz), 3.21 (dd, 1H, J¼15.4, 8.2 Hz), 3.15 (q, 2H,
J¼6.6 Hz), 2.74 (dd, 1H, J¼15.4, 8.2 Hz), 2.66 (t, 2H, J¼6.6 Hz), 2.42
(s, 3H), 1.31 (dd, 1H, J¼14.3, 6.6 Hz), 1.09 (dd, 1H, J¼14.3, 8.8 Hz),
1H), 1.97 (m, 1H), 1.62 (m, 2H). 13C (75 MHz, CDCl3)
d
¼157.9, 141.1,
134.6, 130.0, 128.6, 127.2, 126.7, 126.5, 122.6, 109.8, 104.5, 61.0, 38.7,
22.6, 19.9. HMRS (ESI): calcd for C17H17O2 (MHþ): 253.1223; found:
0.09 (s, 9H). 13C (75 MHz, CDCl3)
d¼158.3, 143.3, 136.8, 129.6, 128.8,
253.1226. Compound 42: 1H (300 MHz, CDCl3)
d
¼6.91 (s, 1H), 6.82
128.0, 127.9, 127.0, 125.1, 109.1, 82.4, 44.5, 38.1, 35.0, 25.2, 21.5, ꢀ0.9.
(s, 1H), 5.89 (d, 1H, J¼6.0 Hz), 3.71 (m, 2H), 3.26 (q, 1H, J¼5.5 Hz),
3.57 (m, 1H), 2.31 (s, 3H), 2.04 (m, 1H), 1.87 (dd, 1H, J¼13.7, 5.0 Hz),
HMRS (ESI): calcd for C21H30NO3SSi (MHþ): 404.1710; found:
404.1720. Compound 52h: 1H (300 MHz, CDCl3)
d
¼7.31 (d, 1H,
1.62 (m, 1H), 1.52 (m, 1H), 1.38 (s, 9H). 13C (75 MHz, CDCl3)
d
¼154.3,
J¼1.7 Hz), 7.27 (dd, 1H, J¼8.2, 1.7 Hz), 6.76 (d,1H, J¼8.2 Hz), 4.92 (m,
1H), 3.29 (dd, 1H, J¼15.4, 8.2 Hz), 2.81 (dd, 1H, J¼15.4, 8.2 Hz), 1.34
(dd, 1H, J¼14.3, 6.6 Hz), 1.11 (dd, 1H, J¼14.3, 8.8 Hz), 0.24 (s, 9H),
132.5, 129.8, 129.5, 125.5, 121.9, 103.5, 60.5, 38.5, 33.9, 29.2, 22.4,
21.1, 19.8. HMRS (ESI): calcd for C16H23O2 (MHþ): 247.1693; found:
247.1693. Compound 44: 1H (300 MHz, CDCl3)
d
¼7.82 (d, 1H, J¼
0.11 (s, 9H). 13C (75 MHz, CDCl3)
d¼160.2, 133.3, 130.5, 129.7, 127.0,
8.2 Hz), 7.71 (d, 1H, J¼8.8 Hz), 7.66 (d, 1H, J¼8.2 Hz), 7.47 (t, 1H,
J¼8.2 Hz), 7.31 (t, 1H, J¼8.2 Hz), 7.16 (d, 1H, J¼8.8 Hz), 6.12 (d, 1H,
J¼6.6 Hz), 3.94 (m, 2H), 3.63 (q, 1H, 7.1 Hz), 2.29 (m, 1H), 1.75 (m,
108.9, 82.2, 38.0, 25.3, ꢀ0.7. HMRS (ESI): calcd for C15H27OSi2
(MHþ): 279.1595; found: 279.1599. Compound 52i: 1H (300 MHz,
CDCl3)
d
¼7.29 (t, 2H, J¼8.2 Hz), 7.02 (t, 1H, J¼8.2 Hz), 6.94 (d, 2H,
2H), 1.57 (m, 1H). 13C (75 MHz, CDCl3)
d
¼154.7, 130.3, 129.4, 129.1,
J¼8.2 Hz), 6.85 (d, 1H, J¼1.7 Hz), 6.79 (dd, 1H, J¼8.2, 1.7 Hz), 6.68 (d,
1H, J¼8.2 Hz), 4.93 (m, 1H), 3.26 (dd, 1H, J¼15.4, 8.2 Hz), 2.79 (dd,
1H, J¼15.4, 8.2 Hz), 1.34 (dd, 1H, J¼14.3, 6.6 Hz), 1.13 (dd, 1H, J¼14.3,
129.0, 126.6, 122.9, 122.4, 122.1, 112.1, 105.6, 61.2, 37.3, 24.0, 20.5.
HMRS (ESI): calcd for C15H15O2 (MHþ): 227.1067; found: 227.1071.
8.8 Hz), 0.10 (s, 9H). 13C (75 MHz, CDCl3)
d¼158.8, 155.7, 149.6,
6.1.4. Cycloaddition with allylsilanes 52
129.4, 128.7, 122.0, 119.3, 117.3, 117.0, 109.3, 82.7, 38.4, 25.2, ꢀ0.8.
HMRS (ESI): calcd for
18H23O2Si (MHþ): 299.1462; found:
299.1455. Compound 57: 1H (300 MHz, CDCl3)
¼7.76 (d, 1H,
A solution of PhI(OAc)2 (‘DIB’, 98 mg, 0.3 mmol, 1.5 equiv) in
(CF3)2CHOH (‘HFIP’, 0.35 ml) was added dropwise over 30 s to
a vigorously stirred solution of phenol 1 (0.2 mmol, 1 equiv) in
allyltrimethylsilane (230 mg, 2 mmol, 10 equiv) and HFIP (0.6 ml).
The mixture was then stirred for 30 s, concentrated under vacuum,
and the residue was purified by silica gel chromatography with
a mixture of ethyl acetate/hexane (5:95). Compound 52a: 1H
C
d
J¼8.2 Hz), 7.63 (d, 1H, J¼8.2 Hz), 7.54 (d, 1H, J¼8.2 Hz), 7.43 (t, 1H,
J¼8.2 Hz), 7.27 (d, 1H, J¼8.2 Hz), 7.05 (d, 1H, J¼8.2 Hz), (m, 1H), 5.10
(m, 1H), 3.56 (dd, 1H, J¼14.8, 8.8 Hz), 3.03 (dd, 1H, J¼14.8, 8.2 Hz),
1.37 (dd,1H, J¼13.7, 6.6 Hz),1.18 (dd,1H, J¼14.3, 8.8 Hz), 0.11 (s, 9H).
13C (75 MHz, CDCl3)
d
¼156.8, 130.8, 128.9, 128.7, 128.6, 126.4, 122.5,
(300 MHz, CDCl3)
d
¼7.31 (d, 1H, J¼1.7 Hz), 7.27 (dd, 1H, J¼8.2,
122.5, 118.5, 112.1, 82.9, 36.9, 25.6, ꢀ0.7. HMRS (ESI): calcd for
16H21OSi (MHþ): 257.1356; found: 257.1350. Compound 59: 1H
(300 MHz, CDCl3)
¼6.35 (s, 2H), 4.92 (m, 1H), 3.84 (s, 3H), 3.77 (s,
1.7 Hz), 6.76 (d, 1H, J¼8.2 Hz), 4.92 (m, 1H), 3.29 (dd, 1H, J¼15.4,
8.2 Hz), 2.81 (dd, 1H, J¼15.4, 8.2 Hz), 1.34 (dd, 1H, J¼14.3, 6.6 Hz),
1.11 (dd, 1H, J¼14.3, 8.8 Hz), 0.24 (s, 9H), 0.11 (s, 9H). 13C (75 MHz,
C
d
3H), 3.22 (dd, 1H, J¼15.4, 8.2 Hz), 2.79 (dd, 1H, J¼15.4, 8.2 Hz), 1.42
CDCl3)
d
¼156.8, 130.8, 128.7, 128.6, 126.4, 122.5, 122.5, 118.5, 112.1,
(dd, 1H, J¼14.3, 6.6 Hz), 1.19 (dd, 1H, J¼14.3, 8.8 Hz), 0.10 (s, 9H). 13
C
82.9, 36.9, 25.6, ꢀ0.7. HMRS (ESI): calcd for C16H27OSi (MHþ):
(75 MHz, CDCl3)
d
¼154.4, 144.3, 141.9, 128.3, 101.4, 99.1, 82.9, 56.0,
263.1826; found: 263.1817. Compound 52b: 1H (300 MHz, CDCl3)
38.9, 30.9, 25.0, ꢀ0.9. HMRS (ESI): calcd for C14H23O3Si (MHþ):
d¼7.32 (d, 1H, J¼1.7 Hz), 7.08 (dd, 1H, J¼8.2, 1.7 Hz), 6.66 (d, 1H,
267.1411; found: 267.1414. Compound 61: 1H (300 MHz, CDCl3)