D. Wang, F.-R. Cao, G. Lu et al.
Tetrahedron xxx (xxxx) xxx
1.51e1.47 (m, 1H) ppm; 13C NMR (151 MHz, CDCl3)
d
¼ 148.1, 145.7,
5.69. 2-(4-Bromothiophen-3-yl)-1,3-dioxolane (4ga) [45]
221.0 mg, 94.0%; Pale yellow liquid. 1H NMR (600 MHz,
127.2, 123.4, 99.9, 67.5, 25.6 ppm. MS (EI, m/z) [M]þ: 209.0.
5.62. 2-(2-Nitrophenyl)-1,3-dioxolane (4ba) [23]
DMSO‑d6) 7.73 (d, J ¼ 3.6 Hz, 1H), 7.71 (d, J ¼ 3.6 Hz, 1H), 5.79 (s,
d
1H), 4.06e4.03 (m, 2H), 3.96e3.93 (m, 2H) ppm; 13C NMR
191.7 mg, 98.3%; Pale yellow liquid. 1H NMR (600 MHz, CDCl3)
(151 MHz, DMSO‑d6)
d
¼ 137.4, 126.3, 125.3, 108.7, 99.0, 64.7 ppm.
d
7.89 (dd, J ¼ 1.2, 7.8 Hz, 1H), 7.80 (dd, J ¼ 1.2, 7.8 Hz, 1H), 7.62 (td,
MS (EI, m/z) [M]þ: 198.0; [Mþ2]þ: 200.0.
J ¼ 7.8, 1.2 Hz, 1H), 7.50 (td, J ¼ 7.8, 1.2 Hz, 1H), 6.48 (s, 1H),
4.08e4.04 (m, 2H), 4.03e4.00 (m, 2H) ppm; 13C NMR (151 MHz,
5.70. 2-(4-Bromothiophen-3-yl)-1,3-dioxane (4gb)
DMSO‑d6)
d
¼ 149.0, 133.5, 132.7, 130.6, 127.9, 124.6, 99.2, 65.2 ppm.
MS (EI, m/z) [M]þ: 195.0.
241.6 mg, 97.0%; Pale yellow liquid. 1H NMR (600 MHz,
DMSO‑d6)
d
7.67 (d, J ¼ 3.6 Hz, 1H), 7.65 (d, J ¼ 3.0 Hz, 1H), 5.46 (s,
5.63. 2-(2-Nitrophenyl)-1,3-dioxane (4bb) [41]
203.8 mg, 97.5%; Pale yellow liquid. 1H NMR (600 MHz, CDCl3)
1H), 4.14e4.10 (m, 2H), 3.94 (td, J ¼ 3.0, 12.6 Hz, 2H), 2.03e1.95 (m,
1H), 1.45e1.41 (m, 1H) ppm; 13C NMR (151 MHz, DMSO‑d6)
d
¼ 138.0,125.6,124.5,108.7, 97.2, 66.7, 25.2 ppm. MS (EI, m/z) [M]þ:
d
7.88 (d, J ¼ 7.8 Hz, 1H), 7.83 (dd, J ¼ 8.4, 1.2 Hz, 1H), 7.61 (td, J ¼ 7.8,
198.0; [Mþ2]þ: 200.0.
1.2 Hz, 1H), 7.47 (td, J ¼ 7.8, 1.2 Hz, 1H), 6.09 (s, 1H), 4.25e4.22 (m,
2H), 4.01 (td, J ¼ 12.6, 2.4 Hz, 2H), 2.23e2.15 (m, 1H), 1.51e1.47 (m,
5.71. 2-Phenethyl-1,3-dioxane (4 hb) [46]
1H) ppm; 13C NMR (151 MHz, CDCl3)
127.7, 124.1, 97.1, 67.6, 25.6 ppm.
d
¼ 148.3, 132.7, 132.6, 129.4,
184.4 mg, 96.0%; Pale yellow liquid. 1H NMR (600 MHz,
DMSO‑d6)
d
7.27 (d, J ¼ 7.8 Hz, 2H), 7.19e7.16 (m, 3H), 4.50 (t,
5.64. 3-Bromo-5-(1,3-dioxan-2-yl)pyridine (4 cb)
J ¼ 4.8 Hz, 1H), 4.02e3.99 (m, 2H), 3.69 (td, J ¼ 12.6, 2.4 Hz, 2H),
2.64e2.60 (m, 2H), 1.91e1.83 (m, 1H), 1.78e1.74 (m, 2H), 1.35e1.31
222.1 mg, 91.0%; Pale yellow liquid. 1H NMR (600 MHz, CDCl3)
(m, 1H) ppm; 13C NMR (151 MHz, DMSO‑d6)
d
¼ 142.0, 128.8, 128.7,
d
8.64 (d, J ¼ 2.4 Hz, 1H), 8.60 (d, J ¼ 1.8 Hz, 1H), 7.98 (t, J ¼ 1.8 Hz,
126.2, 101.1, 66.5, 336.8, 30.0, 25.9 ppm. MS (EI, m/z) [M]þ: 192.1.
1H), 5.53 (s, 1H), 4.29e4.25 (m, 2H), 3.98 (td, J ¼ 2.4, 12.0 Hz, 2H),
2.26e2.17 (m, 1H), 1.49e1.45 (m, 1H) ppm; 13C NMR (151 MHz,
5.72. 2-(2-Chlorophenyl)-1,3-dioxane (4ib) [44]
CDCl3)
d
¼ 150.9, 145.9, 136.7, 135.9, 120.6, 98.6, 67.4, 25.6 ppm. MS
(EI, m/z) [M]þ: 242.9; [Mþ2]þ: 244.9.
188.1 mg, 95.0%; Pale yellow liquid. 1H NMR (600 MHz,
DMSO‑d6)
d
7.62 (dd, J ¼ 7.2, 2.4 Hz, 1H),
d
7.44 (dd, J ¼ 7.8, 1.8 Hz,
5.65. 2-Bromo-5-(1,3-dioxolan-2-yl)pyridine (4da) [42a]
1H), 7.40e7.35 (m, 2H), 5.74 (s, 1H), 4.16 (dd, J ¼ 11.4, 5.4 Hz, 2H),
3.98 (td, J ¼ 12.0, 1.8 Hz, 2H), 2.06e1.98 (m, 1H), 1.46 (d, J ¼ 13.8 Hz,
234.3 mg, 96.0%; Pale yellow liquid. 1H NMR (600 MHz,
DMSO‑d6)
1H) ppm; 13C NMR (151 MHz, DMSO‑d6)
d
¼ 136.4, 132.1, 130.9,
d
8.46 (d, J ¼ 2.4 Hz,1H), 7.80 (dd, J ¼ 8.4, 2.4 Hz,1H), 7.49
129.6, 128.4, 127.6, 98.4, 67.3, 25.7 ppm. MS (EI, m/z) [M]þ: 198.0;
(d, J ¼ 7.71 Hz,1H), 5.84 (s, 1H), 4.08e4.04 (m, 2H), 4.00e3.96 (m,
[Mþ2]þ: 200.0.
2H) ppm; 13C NMR (151 MHz, DMSO‑d6)
d
¼ 148.8, 142.0, 137.8,
133.7, 128.0, 100.4, 65.0 ppm. MS (EI, m/z) [M]þ: 242.9; [Mþ2]þ:
5.73. 2-(Naphthalen-1-yl)-1,3-dioxane (4jb) [47]
244.9.
188.1 mg, 94.0%; Pale yellow liquid. 1H NMR (600 MHz,
5.66. 2-Bromo-5-(1,3-dioxan-2-yl)pyridine (4 db) [42b]
DMSO‑d6)
d
8.27 (d, J ¼ 8.4 Hz, 1H), 7.92 (t, J ¼ 8.4 Hz, 2H), 7.66 (d,
J ¼ 7.2 Hz, 1H), 7.56e7.47 (m, 3H), 6.07 (s, 1H), 4.22 (dd, J ¼ 11.4,
213.9 mg, 93.0%; Pale yellow liquid. 1H NMR (600 MHz, CDCl3)
4.8 Hz, 2H), 4.09 (t, J ¼ 12.0 Hz, 2H), 2.17e2.08 (m, 1H), 1.52 (d,
d
8.43 (d, J ¼ 2.4 Hz, 1H), 7.66 (dd, J ¼ 7.8, 2.4 Hz, 1H), 7.47 (d,
J ¼ 13.8 Hz, 1H) ppm; 13C NMR (151 MHz, DMSO‑d6)
d
¼ 134.3,
J ¼ 8.4 Hz,1H), 5.50 (s, 1H), 4.26e4.23 (m, 2H), 3.98 (td, J ¼ 12.0, 2.4,
133.3, 130.1, 129.0,128.3,125.9,125.7,125.0,124.7, 124.0, 100.0, 68.9,
Hz, 2H), 2.24e2.16 (m, 1H), 1.48e1.44 (m, 1H) ppm; 13C NMR
25.5 ppm. MS (EI, m/z) [[M]þ: 198.0.
(151 MHz, CDCl3)
d
¼ 148.4, 142.3, 136.5, 133.7, 127.7, 98.9, 67.4,
25.6 ppm. MS (EI, m/z) [M]þ: 228.9; [Mþ2]þ: 230.9.
5.67. 2-(3-Methoxyphenyl)-1,3-dioxane (4eb) [43]
184.7 mg, 95.2%; Pale yellow liquid. 1H NMR (600 MHz, CDCl3)
5.74. 2-((4S,5S)-5-methyl-4-(prop-1-en-2-yl)-5-vinylcyclohex-
1-en-1-yl)-1,3-dioxolane (9) [20]
105.5 mg, 90.0%; Pale yellow liquid. 1H NMR (600 MHz, CDCl3)
d
5.79 (dd, J ¼ 16.8, 11.4 Hz, 1H), 4.90 (s, 1H), 4.87 (d, J ¼ 6.0 Hz, 1H),
d
7.28 (t, J ¼ 8.4 Hz, 1H), 7.06e7.05 (m, 2H), 6.89e6.87 (m, 1H), 5.48
4.84 (t, J ¼ 1.8 Hz, 1H), 4.62 (s, 1H), 3.98e3.96 (m, 2H), 3.90e3.88
(m, 2H), 1.98e1.90 (m, 2H), 1.84e1.81 (m, 2H), 1.71 (s, 3H), 1.64 (d,
J ¼ 13.8 Hz,1H),1.59e1.54 (m, 2H),1.52 (dd, J ¼ 13.8, 3.0 Hz,1H),1.10
(s,1H), 4.28e4.25 (m, 2H), 3.99 (td, J ¼ 12.0, 2.4 Hz, 2H), 3.82 (s, 3H),
2.27e2.19 (m, 1H), 1.47e1.43 (m, 1H) ppm; 13C NMR (151 MHz,
CDCl3)
d
¼ 159.6, 140.2, 129.3, 118.4, 15.1, 110.9, 101.5, 67.4, 55.3,
(s, 3H) ppm; 13C NMR (151 MHz, CDCl3)
d
¼ 149.9, 146.8, 112.7, 110.1,
25.8 ppm. MS (EI, m/z) [M]þ: 194.0.
108.7, 77.3, 77.0, 76.8, 64.6, 63.6, 52.2, 46.2, 41.2, 35.5, 27.6, 24.6,
17.8 ppm. MS (EI, m/z) [M]þ: 222.1.
5.68. 2-(4-Chlorophenyl)-1,3-dioxane (4 fb) [44]
186.1 mg, 94.0%; Pale yellow liquid. 1H NMR (600 MHz,
5.75. (3aS,5aS)-6-hydroxy-3a,5a-
dimethyltetradecahydrodicyclopenta[a,f]naphthalen-2(1H)-one
DMSO‑d6)
d
7.41 (d, J ¼ 8.4 Hz, 2H), 7.33 (d, J ¼ 8.4 Hz, 2H), 5.47 (s,
1H), 4.27e4.24 (m, 2H), 3.98 (td, J ¼ 12.6, 2.4 Hz, 2H), 2.25e2.17 (m,
1H), 1.47e1.43 (m, 1H) ppm; 13C NMR (151 MHz, CDCl3)
d
¼ 137.3,
To a stirring solution of Dione 3 (274 mg, 1.0 mmol) in methanol
(2 mL) was added in PVP-I (102 mg, 0.04 mmol effective iodine) and
Trimethyl orthoformate (1.0 mmol, 0.12 mL). The mixture was
134.6, 128.4, 127.5, 100.8, 67.4, 25.7 ppm. MS (EI, m/z) [M]þ: 198.0;
[Mþ2]þ: 200.0.
10