The Journal of Organic Chemistry
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give compound (±)-28 (2.16 g, 95%) as a white solid: R = 0.44 (1:1
solution was degassed three times with CO and heated to 120 °C for
24 h. The reaction mixture was then cooled to room temperature, and
the solvent was concentrated under vacuum. The residue was directly
purified by flash chromatography on silica gel (10:1 petroleum ether/
f
1
petroleum ether/DCM); H NMR (400 MHz, chloroform-d) δ 5.98
(
d, J = 11.8 Hz, 1H), 5.88 (dd, J = 11.7, 8.8 Hz, 1H), 5.10 (dt, J = 2.2,
.1 Hz, 1H), 5.07 (p, J = 1.6 Hz, 1H), 4.43 (t, J = 8.8 Hz, 1H), 3.10
1
(
dd, J = 11.2, 4.4 Hz, 1H), 2.54−2.44 (m, 1H), 2.27 (s, 1H), 1.99−
DCM) to give compound (±)-31 (32 mg, 32%) as a white solid: R =
f
1
1
6
0
1
3
.90 (m, 1H), 1.93 (s, 3H), 1.66 (d, J = 8.7 Hz, 1H), 1.70−1.45 (m,
0.66 (1:1 petroleum ether/DCM); H NMR (400 MHz, chloroform-
H), 1.35−1.27 (m, 1H), 0.88 (s, 9H), 0.87 (s, 3H), 0.84 (s, 3H),
d) δ 9.83 (s, 1H), 7.25 (d, J = 8.3 Hz, 2H), 7.18 (d, J = 8.1 Hz, 2H),
3.23 (dd, J = 11.3, 4.6 Hz, 1H), 2.54 (ddd, J = 13.8, 9.8, 4.5 Hz, 1H),
2.34 (s, 3H), 2.16 (dddd, J = 13.2, 11.8, 4.7, 1.2 Hz, 1H), 2.10−1.97
(m, 2H), 1.81−1.69 (m, 2H), 1.67−1.53 (m, 2H), 1.44 (dd, J = 12.1,
8.3 Hz, 1H), 0.90 (s, 9H), 0.89 (s, 3H), 0.84 (s, 3H), 0.74 (s, 3H),
1
3
1
.02 (s, 3H), 0.01 (s, 3H); C{ H} NMR (100 MHz, CDCl ) δ
3
41.4, 133.4, 132.3, 116.8, 87.2, 80.2, 73.6, 68.7, 55.3, 52.9, 46.9, 39.4,
3.4, 32.0, 30.1, 29.1, 26.0, 22.9, 21.0, 19.7, 18.3, 16.3, −3.8, −4.8; IR
(
neat) ν = 3305, 2953, 2928, 2884, 2856, 1472, 1461, 1385, 1361,
max
1
3
1
1
252, 1118, 1091, 1065, 1050, 1006, 983, 970, 880, 834, 772, 622
0.054 (s, 3H), 0.047 (s, 3H); C{ H} NMR (100 MHz, CDCl ) δ
3
−
1
+
cm ; HRMS (ESI) m/z calcd for C H NaO Si [M + Na]
202.8, 136.8, 135.2, 129.6, 128.6, 79.6, 67.9, 54.0, 48.6, 39.5, 31.9,
2
6
44
2
4
39.3003, found 439.2999.
Synthesis of Compound 29. To a solution of compound 28
28.9, 28.7, 26.0, 25.5, 21.1, 19.4, 18.3, 17.0, 15.8, −3.8, −4.8; IR
(neat) ν = 2951, 2928, 2882, 2855, 2736, 1713, 1513, 1471, 1461,
max
(
°
(
500 mg, 1.20 mmol, 1.0 equiv) in anhydrous DCM (12 mL) at −40
1385, 1360, 1251, 1108, 1091, 1060, 1005, 912, 880, 835, 812, 773
−
1
+
C were added Et N (0.50 mL, 3.60 mmol, 3.0 equiv) and TBSOTf
cm ; HRMS (ESI) m/z calcd for C H O Si [M + H] 415.3027,
3
26 43 2
0.41 mL, 1.80 mmol, 1.5 equiv) in sequence. The reaction mixture
found 415.3026.
was warmed to room temperature and stirred for 2 h before the
reaction was quenched by adding a saturated solution of NaHCO3
Synthesis of Compound 32. To a solution of compound 29
(200 mg, 0.377 mmol, 1.0 equiv) in anhydrous toluene (19 mL)
under N was added Co (CO) (142 mg, 0.414 mmol, 1.1 equiv) at
(
20 mL). The resultant mixture was extracted with petroleum ether (3
20 mL). The combined organic layer was dried over Na SO and
2
2
8
×
room temperature. The mixture was degassed three times with N and
2
4
2
concentrated under vacuum. The residue was purified by flash
stirred at room temperature for 12 h. The resultant dark brown
solution was degassed three times with CO and heated to 120 °C for
24 h. The reaction mixture was then cooled to room temperature, and
the solvent was concentrated under vacuum. The residue was directly
purified by flash chromatography on silica gel (petroleum ether) to
chromatography on silica gel (petroleum ether) to give compound
(
±)-29 (542 mg, 85%) as a viscous colorless oil: R = 0.35 (petroleum
f
1
ether); H NMR (400 MHz, chloroform-d) δ 5.85 (dt, J = 12.2, 1.0
Hz, 1H), 5.53 (dd, J = 12.1, 10.1 Hz, 1H), 5.16−5.14 (m, 1H), 5.07
(dd, J = 10.1, 0.8 Hz, 1H), 5.01 (dp, J = 3.6, 1.2 Hz, 1H), 3.32 (dd, J
give compound (±)-32 (131 mg, 66%) as a white solid: R = 0.45
f
1
=
10.8, 4.6 Hz, 1H), 2.41 (dt, J = 13.6, 8.4 Hz, 1H), 2.18 (s, 1H), 2.06
(20:1 petroleum ether/DCM); H NMR (400 MHz, chloroform-d) δ
(
dd, J = 11.5, 8.4 Hz, 1H), 1.94 (s, 3H), 1.89−1.81 (m, 1H), 1.79−
5.62 (dt, J = 5.4, 2.2 Hz, 1H), 5.54−5.48 (m, 1H), 3.63 (d, J = 6.5 Hz,
1H), 3.16 (dd, J = 11.3, 4.4 Hz, 1H), 2.85−2.75 (m, 1H), 2.61−2.50
(m, 1H), 2.47 (ddd, J = 13.0, 9.4, 4.9 Hz, 1H), 2.37 (dt, J = 20.6, 5.6
Hz, 1H), 1.79 (ddd, J = 12.9, 11.2, 4.7 Hz, 1H), 1.69 (s, 3H), 1.74−
1.62 (m, 1H), 1.59−1.42 (m, 3H), 1.38 (dt, J = 12.8, 3.5 Hz, 1H),
1.32−1.25 (m, 2H), 1.01 (s, 3H), 0.90 (s, 9H), 0.89 (s, 9H), 0.822 (s,
3H), 0.816 (s, 3H), 0.10 (s, 3H), 0.09 (s, 3H), 0.02 (s, 3H), 0.01 (s,
1
1
0
.65 (m, 2H), 1.64−1.48 (m, 3H), 1.45 (dt, J = 11.1, 2.5 Hz, 1H),
.14 (s, 3H), 0.90 (s, 9H), 0.89 (s, 9H), 0.88 (s, 3H), 0.83 (s, 3H),
1
3
1
.07 (s, 3H), 0.06 (s, 3H), 0.03 (s, 3H), 0.01 (s, 3H); C{ H} NMR
100 MHz, CDCl ) δ 141.6, 132.7, 131.0, 118.1, 89.0, 79.6, 73.8, 70.0,
(
3
5
2
2
1
3.7, 52.0, 47.6, 39.5, 31.8, 30.7, 29.8, 29.4, 26.3, 26.1, 23.7, 22.4,
0.7, 18.4, 18.3, 17.1, −2.9, −3.6, −3.8, −4.8; IR (neat) ν = 3308,
max
1
3
1
953, 2928, 2883, 2856, 1471, 1462, 1385, 1360, 1251, 1118, 1081,
3H); C{ H} NMR (100 MHz, CDCl ) δ 138.7, 135.0, 120.3, 112.8,
3
−
1
063, 1046, 1005, 880, 859, 834, 773, 628 cm ; HRMS (ESI) m/z
80.7, 72.2, 67.2, 52.5, 48.7, 45.3, 39.3, 31.9, 31.2, 29.0, 28.7, 27.6,
+
calcd for C H O Si [M + H] 531.4048, found 531.4049.
26.1, 25.9, 23.3, 20.9, 18.3, 17.9, 17.6, 15.8, −3.81, −3.82, −4.7, −4.9;
32
59
2
2
Synthesis of Compound 30. To a solution of compound 28
IR (neat) ν = 2952, 2928, 2896, 2885, 2855, 2814, 1471, 1462,
max
(
300 mg, 0.720 mmol, 1.0 equiv) in anhydrous DCM (10 mL) were
1442, 1380, 1360, 1252, 1118, 1101, 1076, 1058, 1004, 934, 880, 835,
−
1
added DMAP (44.0 mg, 0.360 mmol, 0.50 equiv) and Et N (0.60 mL,
4
820, 772, 677 cm ; HRMS (ESI) m/z calcd for C H O Si [M +
3
32 59 2 2
+
.32 mmol, 6.0 equiv) in sequence. The mixture described above was
H] 531.4048, found 531.4050.
cooled to 0 °C, and Ac O (0.20 mL, 2.16 mmol, 3.0 equiv) was
added. The reaction mixture was warmed to room temperature and
stirred for 6 h before the reaction was quenched by adding a saturated
Synthesis of Compounds 33 and 34. To a 1.0 L round-bottom
flask was added a solution of compound 32 (119 mg, 0.224 mmol, 1.0
equiv) in petroleum ether (50 mL). The solvent was removed under
vacuum by rotary evaporators, making compound 32 disperse on the
flask wall. The flask was then placed in the dark under air for 3 days.
The residue was purified by flash chromatography on silica gel (50:1
petroleum ether to petroleum ether/DCM) to give compound
(±)-33 (30 mg, 27%) as a white solid and (±)-34 (12 mg, 9%) as a
colorless solid.
2
solution of NaHCO (20 mL). The resultant mixture was extracted
3
with ethyl acetate (3 × 20 mL). The combined organic layer was
dried over Na SO and concentrated under vacuum. The residue was
2
4
purified by flash chromatography on silica gel (petroleum ether/
DCM) to give compound (±)-30 (337 mg, 99%) as a white solid: Rf
1
=
0.59 (1:1 petroleum ether/DCM); H NMR (400 MHz,
chloroform-d) δ 7.26 (s, 0H), 6.03 (dd, J = 10.1, 0.8 Hz, 1H), 5.98
d, J = 11.9 Hz, 1H), 5.70 (dd, J = 11.9, 10.0 Hz, 1H), 5.08 (s, 1H),
Data of Compound (±)-33. R = 0.60 (10:1 petroleum ether/
f
1
(
DCM); H NMR (400 MHz, chloroform-d) δ 7.05 (s, 1H), 7.04 (s,
5
2
.06 (p, J = 1.7 Hz, 1H), 3.13 (dd, J = 11.1, 4.6 Hz, 1H), 2.29 (s, 1H),
.06 (s, 3H), 2.11−1.91 (m, 2H), 1.97 (s, 3H), 1.70 (dd, J = 12.7, 7.6
1H), 6.92 (s, 1H), 5.14 (s, 1H), 3.21 (dd, J = 11.2, 4.3 Hz, 1H), 2.42
(ddd, J = 13.7, 8.9, 6.0 Hz, 1H), 2.33 (d, J = 0.7 Hz, 3H), 1.84 (ddd, J
= 13.7, 10.1, 5.5 Hz, 1H), 1.76−1.65 (m, 1H), 1.63−1.43 (m, 4H),
1.43−1.33 (m, 1H), 1.19 (dt, J = 12.8, 3.7 Hz, 1H), 1.12 (s, 3H), 0.95
(s, 9H), 0.90 (s, 9H), 0.89 (s, 3H), 0.87 (s, 3H), 0.204 (s, 3H), 0.198
Hz, 1H), 1.67−1.48 (m, 4H), 1.45 (dd, J = 13.0, 3.9 Hz, 1H), 1.36
(
0
dt, J = 12.8, 3.3 Hz, 1H), 1.13 (s, 3H), 0.89 (s, 3H), 0.88 (s, 9H),
.84 (s, 3H), 0.02 (s, 3H), 0.01 (s, 3H); C{ H} NMR (100 MHz,
1
3
1
1
3
1
CDCl ) δ 169.8, 141.6, 134.4, 127.3, 117.8, 86.7, 80.3, 73.7, 71.1,
(s, 3H), 0.04 (s, 6H); C{ H} NMR (100 MHz, CDCl ) δ 147.0,
3
3
5
1
2
9
3.4, 52.6, 47.9, 39.4, 33.5, 31.2, 30.2, 29.0, 26.0, 22.7, 21.6, 21.3,
144.4, 137.3, 129.6, 123.4, 122.7, 80.7, 71.9, 68.6, 53.7, 45.9, 39.4,
30.4, 29.6, 29.2, 28.6, 26.1, 26.0, 22.2, 21.3, 18.31, 18.30, 17.7, 15.5,
9.7, 18.3, 16.2, −3.8, −4.9; IR (neat) ν = 3307, 2953, 2928, 2886,
max
856, 1737, 1472, 1461, 1385, 1367, 1227, 1120, 1086, 1049, 1013,
−3.8, −3.9, −4.6, −4.8; IR (neat) ν = 2951, 2928, 2894, 2856,
max
−
1
55, 906, 879, 833, 772, 629 cm ; HRMS (ESI) m/z calcd for
1471, 1462, 1380, 1361, 1327, 1251, 1152, 1138, 1120, 1102, 1080,
+
−1
C H O Si [M + H] 459.3289, found 459.3300.
1053, 1005, 889, 878, 835, 816, 772, 676 cm ; HRMS (ESI) m/z
28
47
3
+
Synthesis of Compound 31. To a solution of compound 28
100 mg, 0.240 mmol, 1.0 equiv) in anhydrous toluene (12 mL)
under N was added Co (CO) (90.3 mg, 0.264 mmol, 1.1 equiv) at
calcd for C H O Si [M + H] 529.3892, found 529.3895.
3
2
57
2
2
(
Data of Compound (±)-34. R = 0.39 (10:1 petroleum ether/
f
1
DCM); H NMR (500 MHz, chloroform-d) δ 7.26 (d, J = 8.2 Hz,
2
2
8
room temperature. The mixture was degassed three times with N and
stirred at room temperature for 12 h. The resultant dark brown
2H), 7.06 (d, J = 8.0 Hz, 2H), 4.74 (s, 1H), 4.01 (dd, J = 11.6, 4.3 Hz,
1H), 3.11 (td, J = 13.5, 4.3 Hz, 1H), 2.31 (s, 3H), 2.13 (td, J = 11.7,
2
2
148
J. Org. Chem. 2021, 86, 2135−2157