334 JOURNAL OF CHEMICAL RESEARCH 2016
reaction mixture was cooled to –78 °C and the above crude aldehyde
6 in dry THF (2 mL) was added over a period of 5 min. The resulting
mixture was stirred for 1 h at –78 °C. The reaction mixture was then
treated with a saturated solution of ammonium chloride and extracted
with EtOAc. The combined organic phases were dried with Na2SO4
and concentrated under reduced pressure. The crude product was
purified by flash column chromatography to give compound 11 as
(d, J = 6.0 Hz, 1H), 4.72 (m, 1H), 5.82 (dt, J = 11.6 Hz, 2.0 Hz, 1H),
6.23 (dt, J = 11.6 Hz, 7.2 Hz, 1H), 7.42 (m, 5H); 13C NMR (100 MHz,
CDCl3) δ 166.7, 145.0, 140.1, 128.7, 128.4, 127.2, 123.0, 108.6, 80.5,
75.6, 72.1, 51.4, 32.9, 27.7, 25.2; HRMS (ESI-TOF) m/z for C17H22O5Na
[M + Na]+ calcd 329.1365; found: 329.1388.
Synthesis of 7-epi-goniodiol (3)
a colourless oil (490 mg, 73% for the two steps). [α]25 + 6.1 (c 2.5,
A solution of ester 5 (27 mg, 0.088 mmol) in MeOH (5 mL) was
treated with p-toluenesulfonic acid monohydrate (3.6 mg, 0.019
mmol) at room temperature. The mixture was stirred overnight and
concentrated under reduced pressure. The crude was purified by flash
column chromatography to give 7-epi-goniodiol (3) (16.7 mg, 81%).
[α]25D = +82.5 (c 0.6, MeOH); lit.,12 [α]30D = +84.2 (c 0.4, MeOH); IR
(film, cm–1): 3450, 2985, 1716, 1629, 1380, 1209, 1067, 1029; 1H NMR
(400 MHz, CDCl3): δ 2.50 (m, 1 H), 2.59 (m, 1H), 2.86 (br s, 1H), 3.95
(dd, J = 4.4 Hz, 5.6 Hz, 1H), 4.44 (m, 1H), 4.91 (d, J = 4.4 Hz, 1H), 5.98
(ddd, J = 10.0 Hz, 2.8 Hz, 1.2 Hz, 1H), 6.90 (ddd, J = 10.0 Hz, 6.0 Hz,
2.4 Hz, 1H), 7.36 (m, 5H); 13C NMR (100 MHz, CDCl3) δ 164.0, 145.8,
140.2, 128.7, 128.1, 126.3, 120.9, 77.4, 76.1, 29.6; HRMS (ESI-TOF)
m/z for C13H14O4Na [M + Na]+ calcd 257.0790; found: 257.0794.
D
CHCl3); IR (film, cm–1): 2949, 2928, 2884, 1724 (C=O), 1650, 1438,
1
1376, 1250, 1190, 1172; H NMR (400 MHz): δ 0.07 (s, 6H), 0.88 (s,
9H), 1.33 (s, 3H), 1.41 (s, 3H), 2.86 (m, 1H), 3.02 (m, 1H), 3.68 (s, 3H),
3.70 (dd, J = 12.0 Hz, 6.0 Hz, 1H), 4.17 (m, 1H), 4.24 (ddd, J = 9.0 Hz,
J = 6.0 Hz, 4.0 Hz, 1H), 5.88 (dt, J = 11.6 Hz, 1.8 Hz, 1H), 6.36 (dt,
J = 11.6 Hz, 6.8 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 166.4, 146.4,
120.5, 108.1, 77.8, 76.7, 61.7, 50.9, 29.5, 27.9, 25.8, 25.3, 18.1, –5.5;
HRMS (ESI-TOF) m/z for C17H32SiO5Na [M + Na]+ calcd 367.1917;
found: 367.1965.
Synthesis of (Z)-methyl4-((4R,5S)-5-(hydroxymethyl)-2,2-dimethyl-
1,3-dioxolan-4-yl) but-2-enoate (12)
A solution of 11 (238 mg, 0.69 mmol) in THF (10 mL) was treated with
hydrogen fluoride pyridine complex (ca 70% HF, 110 mg) under an N2
atmosphere. After stirring for 2 h at room temperature, the reaction
mixture was quenched with saturated aqueous NaHCO3 and extracted
with EtOAc. The combined organic phase was washed with brine,
dried over Na2SO4 and concentrated under vacuum. The crude product
was purified by flash column chromatography to give compound 12 as
This work was supported by the National Natural Science
Foundation of China (21302150) and Hubei Provincial
Department of Education (D20131501). The authors declare
that they have no conflict of interest.
a colourless oil (158 mg, 98%). [α]25 +19.0 (c 1.2, CHCl3); IR (film,
Received 15 January 2016; accepted 29 February 2016
Published online: 1 June 2016
D
cm–1): 3448, 2952, 1723, 1658, 1440, 1384, 1382, 1275, 1220, 1041;
1H NMR (400 MHz): δ 1.36 (s, 3H), 1.47 (s, 3H), 2.24 (br s, 1H), 2.82
(m, 1H), 3.69 (d, J = 5.6 Hz, 1H), 3.71 (s, 3H), 4.27 (m, 1H), 5.90 (dt,
J = 11.6 Hz, 2.0 Hz, 1H), 6.36 (dt, J = 11.6 Hz, 8.0 Hz, 1H); 13C NMR
(100 MHz, CDCl3) δ 166.7, 146.0, 120.9, 108.4, 77.8, 76.3, 61.4, 51.1,
29.2, 27.9, 25.4; HRMS (ESI-TOF) m/z for C11H18O5Na [M + Na]+
calcd 253.1052; found: 253.1075.
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