Y. Gao, J. Liu, L. Wang, M. Xiao, Y. Du
FULL PAPER
then mercuric acetate (956 mg, 2.686 mmol) in cooled water
(10 mL) was added dropwise. The suspension was stirred for 1 h
and then 8 % aqueous KI solution (10 mL) was then added to
quench the reaction. The reaction mixture was extracted with
EtOAc (3ϫ 20 mL) and the combined organic solvents were dried
with anhydrous Na2SO4 and concentrated in vacuo to afford the
crude aldehyde. Purification on silica gel (EtOAc/petroleum ether,
1:16) afforded 17 (287 mg, 75%) as a colorless oil. [α]2D5 = –148 (c
(S)-Pent-4-en-2-yl 2-{(E)-3-[(4S,5S)-5-{(S)-1-[(tert-Butyldimethyl-
silyl)oxy]allyl}-2,2-dimethyl-1,3-dioxolan-4-yl]prop-1-en-1-yl}-6-
hydroxy-4-methoxybenzoate (19): To a solution of pent-4-en-2-ol
(11; 90 mg, 1.046 mmol) in dry THF was added NaH (62 mg, 60%
in mineral oil, 1.55 mmol) under nitrogen at 0 °C. The reaction
mixture was stirred at this temperature for 30 min and then a solu-
tion of 18 (100 mg, 0.193 mmol) in THF (5 mL) was added to the
above suspension. Saturated aqueous NH4Cl (2 mL) was added to
= 0.3, CHCl3). 1H NMR (400 MHz, CDCl3): δ = 9.77 (s, 1 H), quench the reaction until TLC showed completion of the reaction
5.99–5.92 (m, 1 H), 5.32 (dd, J = 17.2, 1.2 Hz, 1 H), 5.22 (dd, J =
10.8, 1.2 Hz, 1 H), 4.70–4.64 (m, 1 H), 4.23–4.21 (m, 1 H), 4.13–
4.10 (m, 1 H), 2.89–2.83 (m, 2 H), 1.47 (s, 3 H), 1.35 (s, 3 H), 0.89
(d, J = 1.6 Hz, 9 H), 0.07 (dd, J = 2.0 Hz, 6 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 200.76, 137.14, 117.01, 108.75, 79.56,
73.27, 72.16, 44.16, 27.46, 26.04, 25.41, 18.48, –4.38, –4.64 ppm.
(about 4 h). The mixture was extracted with EtOAc (3ϫ 5 mL),
concentrated under reduced pressure, and the residue purified by
silica gel column chromatography (EtOAc/petroleum ether, 1:25) to
afford 19 (79 mg, 75%) as a colorless oil. [α]2D5 = –59.4 (c = 0.65,
1
CHCl3). H NMR (400 MHz, CDCl3): δ = 11.74 (s, 1 H), 7.04 (d,
J = 15.6 Hz, 1 H), 6.48 (d, J = 2.8 Hz, 1 H), 6.38 (d, J = 2.4 Hz,
1 H), 6.04–5.92 (m, 2 H), 5.86–5.76 (m, 1 H), 5.35 (d, J = 17.6 Hz,
1 H), 5.27–5.20 (m, 2 H), 5.15–5.10 (m, 2 H), 4.28–4.27 (m, 1 H),
4.18 (ddd, J = 9.6, 6.0, 3.6 Hz, 1 H), 4.03 (t, J = 6.0 Hz, 1 H), 3.81
(s, 3 H), 2.63–2.38 (m, 4 H), 1.50 (s, 3 H), 1.35 (d, J = 6.4 Hz, 3
IR: ν = 2936, 2857, 1725, 1655, 1473 cm–1. HRMS (ESI): calcd.
˜
for C16H30O4SiNa [M + Na]+ 337.1811; found 337.1775.
tert-Butyl{[(S)-1-{(4S,5S)-5-[(E)-3-iodoallyl]-2,2-dimethyl-1,3-di-
oxolan-4-yl}allyl]oxy}dimethylsilane (10): Anhydrous CrCl2
(626 mg, 5.088 mmol) was suspended in dry THF (15 mL) under
nitrogen. A solution of aldehyde 17 (200 mg, 0.636 mmol) and
iodoform (752 mg, 1.908 mmol) in THF (8 mL) was then added
dropwise to the suspension at 0 °C. After stirring at 0 °C for 3 h,
the reaction mixture was poured into water (10 mL), extracted with
diethyl ether (3ϫ 25 mL), and evaporated in vacuo. The residue
was purified by silica gel chromatography (EtOAc/petroleum ether,
H), 1.34 (s, 3 H), 0.92 (s, 9 H), 0.10 (s, 3 H), 0.09 (s, 3 H) ppm. 13
C
NMR (100 MHz, CDCl3): δ = 170.92, 165.13, 164.11, 143.51,
137.62, 133.52, 133.32, 129.15, 118.40, 116.70, 108.52, 108.30,
104.21, 99.96, 80.72, 73.30, 72.00, 55.60, 40.38, 33.73, 29.89, 27.88,
26.07, 25.71, 19.79, 18.52, –4.28, –4.51 ppm. IR: ν = 2933,
˜
2857, 1743, 1649, 1611, 1581 cm–1. HRMS (ESI): calcd. for
C30H46O7SiNa [M + Na]+ 569.2911; found 569.2890.
1:250) to afford vinyl iodide 10 (181 mg, 65%) as a colorless oil. (S)-Pent-4-en-2-yl 2-Hydroxy-6-[(E)-3-{(4S,5R)-5-[(S)-1-
[α]2D5 = –150 (c = 0.6, CHCl3). 1H NMR (400 MHz, CDCl3): δ =
6.59 (dt, J = 14.4, 7.2 Hz, 1 H), 6.09 (d, J = 14.4 Hz, 1 H), 5.91
(ddd, J = 16.8, 10.4, 5.6 Hz, 1 H), 5.32 (d, J = 17.6 Hz, 1 H), 5.19
(d, J = 10.4 Hz, 1 H), 4.22 (t, J = 6.4 Hz, 1 H), 4.11–4.07 (m, 1
H), 3.99 (t, J = 6.4 Hz, 1 H), 2.41–2.36 (m, 2 H), 1.47 (s, 3 H), 1.33
hydroxyallyl]-2,2-dimethyl-1,3-dioxolan-4-yl}prop-1-en-1-yl]-4-meth-
oxybenzoate (8): A solution of 19 (90 mg, 0.165 mmol) in THF
(5 mL) was treated with TBAF (60 mg, 0.189 mmol) at room temp.
After the starting material had disappeared, the solvent was re-
moved and the residue subjected directly to silica gel column
(s, 3 H), 0.90 (s, 9 H), 0.08 (s, 3 H), 0.07 (s, 3 H) ppm. 13C NMR chromatography (EtOAc/petroleum ether, 1:3) to afford 8 (58 mg,
1
(100 MHz, CDCl3): δ = 143.21, 137.24, 116.93, 108.48, 80.54,
82%) as a colorless oil. [α]2D5 = +33.3 (c = 0.3, CHCl3). H NMR
(400 MHz, CDCl3): δ = 11.74 (s, 1 H), 7.07 (d, J = 15.6 Hz, 1 H),
6.45 (d, J = 2.4 Hz, 1 H), 6.39 (d, J = 2.8 Hz, 1 H), 5.95–5.78 (m,
3 H), 5.42 (d, J = 17.6 Hz, 1 H), 5.30–5.23 (m, 2 H), 5.16–5.10 (m,
2 H), 4.30–4.27 (m, 1 H), 4.22–4.21 (m, 1 H), 4.07 (t, J = 5.6 Hz,
1 H), 3.82 (s, 3 H), 2.68–2.62 (m, 1 H), 2.56–2.40 (m, 3 H), 2.36
(d, J = 5.6 Hz, 1 H), 1.53 (s, 3 H), 1.38 (s, 3 H), 1.36 (d, J = 6.4 Hz,
3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 170.72, 165.11,
164.04, 143.19, 137.37, 133.75, 133.44, 128.03, 118.32, 117.57,
108.51, 108.33, 104.18, 99.95, 79.89, 71.99, 70.83, 55.49, 40.26,
76.38, 72.95, 36.74, 27.87, 26.03, 25.68, 18.50, –4.32, –4.54 ppm.
IR: ν = 2933, 2857, 1614, 1470 cm–1. HRMS (ESI): calcd. for
˜
C17H31O3ISiNa [M + Na]+ 461.0985; found 461.0964.
5-{(E)-3-[(4S,5S)-5-{(S)-1-[(tert-Butyldimethylsilyl)oxy]allyl}-2,2-di-
methyl-1,3-dioxolan-4-yl]prop-1-en-1-yl}-7-methoxy-2,2-dimethyl-
4H-benzo[d][1,3]dioxin-4-one (18): Degassed solvent (THF/H2O,
10:1, 11 mL) was added under nitrogen to a mixture of vinyl iodide
10 (144 mg, 0.328 mmol), boronate 9 (141 mg, 0.422 mmol),
Cs2CO3 (426 mg, 1.308 mmol), and [Pd(PPh3)4] (cat.). The solution
was heated at 70 °C for 2 h (monitoring with TLC). After cooling
to room temp., saturated aqueous NH4Cl (5 mL) was added and
the mixture extracted with EtOAc (3ϫ 10 mL). The organic layer
was dried with Na2SO4 and then concentrated to dryness. The resi-
due was purified by silica gel column chromatography (EtOAc/pe-
33.81, 27.70, 25.18, 19.72 ppm. IR: ν = 3440, 2924, 2851, 2320,
˜
1728, 1461 cm–1. HRMS (ESI): calcd. for C24H32O7Na [M + Na]+
455.2046; found 455.2039.
(3aS,4S,5E,8S,15E,17aS)-4-(tert-Butyldimethylsilyloxy)-11-
hydroxy-13-methoxy-2,2,8-trimethyl-7,8,17,17a-tetrahydro-3aH-
troleum ether, 1:6) to afford 18 (116 mg, 68%) as a yellowish oil. benzo[c][1,3]dioxolo[4,5-h][1]oxacyclotetradecin-10(4H)-one (21):
1
[α]2D5 = –163.3 (c = 0.6, CHCl3). H NMR (400 MHz, CDCl3): δ =
7.51 (d, J = 16.0 Hz, 1 H), 6.79 (d, J = 2.4 Hz, 1 H), 6.33 (d, J = added to a solution of 19 (60 mg, 0.11 mmol) in degassed dry
2.4 Hz, 1 H), 6.27 (dt, J = 17.6, 7.2 Hz, 1 H), 5.93 (ddd, J = 16.8, CH2Cl2 (180 mL). The mixture was stirred at 40 °C for 12 h, the
The second-generation Grubbs catalyst (12 mg, 0.015 mmol) was
10.4, 6.0 Hz, 1 H), 5.37 (d, J = 17.6 Hz, 1 H), 5.21 (d, J = 10.4 Hz, solvent was removed under reduced pressure, and the residue puri-
1 H), 4.29 (t, J = 6.8 Hz, 1 H), 4.20 (ddd, J = 9.6, 5.6, 4.0 Hz, 1 fied by silica gel column chromatography (EtOAc/petroleum ether,
H), 4.01 (t, J = 6.0 Hz, 1 H), 3.84 (s, 3 H), 2.63–2.57 (m, 2 H), 1.69
(s, 6 H), 1.51 (s, 3 H), 1.35 (s, 3 H), 0.91 (s, 9 H), 0.11 (s, 3 H),
0.08 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 164.93,
1:25) to afford 21 (38.1 mg, 67%) as a colorless oil. [α]2D5 = –112.2
(c = 0.18, CHCl3). 1H NMR (400 MHz, CDCl3): δ = 11.69 (s, 1
H), 6.88 (d, J = 15.6 Hz, 1 H), 6.39 (d, J = 2.4 Hz, 1 H), 6.37 (d,
160.43, 158.84, 144.01, 137.38, 135.39, 131.67, 130.31, 117.04, J = 2.4 Hz, 1 H), 5.86 (ddd, J = 15.2, 7.6, 4.8 Hz, 1 H), 5.76 (ddd,
108.44, 108.38, 105.13, 103.88, 100.47, 81.12, 77.40, 72.97, 55.81, J = 15.2, 7.2, 4.0 Hz, 1 H), 5.56 (dd, J = 15.6, 8.0 Hz, 1 H), 5.39–
34.04, 29.88, 28.02, 26.08, 25.90, 25.83, 25.80, 18.56, –4.23, 5.35 (m, 1 H), 4.28 (t, J = 8.4 Hz, 1 H), 4.15–4.11 (m, 1 H), 3.99
–4.46 ppm. IR: ν = 2927, 2854, 1734, 1608, 1576 cm–1. HRMS (dd, J = 8.8, 5.2 Hz, 1 H), 3.81 (s, 3 H), 2.68–2.44 (m, 4 H), 1.49
˜
(ESI): calcd. for C28H42O7SiNa [M + Na]+ 541.2597; found
541.2603.
(s, 3 H), 1.42 (d, J = 6.4 Hz, 3 H), 1.36 (s, 3 H), 0.86 (s, 9 H), 0.09
(s, 3 H), 0.05 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
2096
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Eur. J. Org. Chem. 2014, 2092–2098