The Journal of Organic Chemistry
Page 22 of 29
yellow oil and as an inseparable mixture of diastereoisomers (d. r. = 1:1); 1H NMR (400 MHz, CDCl3) δ
7.45 – 7.39 (m, 5H), 5.59 (ddd, J = 12.7, 7.9, 4.6 Hz, 1H), 4.42 (qd, J = 8.4, 6.2 Hz, 1H), 3.77 (s, 1.5H),
3.67 (d, J = 12.5 Hz, 3H), 3.53 (s, 1.5H), 2.98 – 2.81 (m, 2H) ppm; 13C{1H} NMR (101 MHz, CDCl3) δ
169.3, 169.0, 168.5, 168.4, 165.2 (d, J = 3.0 Hz), 165.1 (d, J = 2.8 Hz), 129.7, 129.6, 129.4, 129.0,
128.9, 128.7 (d, J = 0.9 Hz), 123.6 (q, J = 279.5 Hz), 123.5 (q, J = 279.7 Hz), 69.5, 69.4, 55.3 (q, J =
29.3 Hz), 55.2 (q, J = 29.2 Hz), 52.9, 52.8, 52.3, 52.1, 35.7 ppm; 19F{1H} NMR (376 MHz, CDCl3) δ -
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70.7 (s, 1.5F), -70.8 (s, 1.5F) ppm; HRMS-ESI m/z : [M-H]- calcd for C15H14F3O6 347.0748, found
347.0749.
(3aR,5R,6S,6aR)-5-((R)-2,2-Dimethyl-1,3-dioxolan-4-yl)-2,2-dimethyltetrahydrofuro[2,3-
d][1,3]dioxol-6-yl 3,3,3-trifluoro-2-phenylpropanoate (5q). The product (115.5 mg, 52% yield) was
purified with silica gel chromatography (petroleum ether/dichloromethane = 1/1) as a colorless oil and
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as an inseparable mixture of diastereoisomers (d. r. = 1:1); H NMR (400 MHz, CDCl3) δ 7.46 – 7.40
(m, 5H), 5.88 (d, J = 3.5 Hz, 0.5H), 5.74 (d, J = 3.6 Hz, 0.5H), 5.40 – 5.39 (m, 1H), 4.50 (d, J = 3.6 Hz,
0.5H), 4.40 – 4.32 (m, 1.5H), 4.19 (s, 1H), 4.13 (dd, J = 8.2, 2.7 Hz, 1H), 3.99 – 3.96 (m, 0.5H), 3.91 –
3.82 (m, 1H), 3.78 (dt, J = 8.2, 5.5 Hz, 0.5H), 1.51 (s, 3H), 1.41 (s, 1.5H), 1.31 (dd, J = 14.2, 10.2 Hz,
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6H), 1.10 (s, 1.5H) ppm; C{1H} NMR (101 MHz, CDCl3) δ 164.9 (d, J = 2.8 Hz), 164.7 (d, J = 2.6
Hz), 129.6, 129.53, 129.50, 129.14, 129.09, 128.9 (d, J = 1.0 Hz), 123.6 (q, J = 280.0 Hz), 112.7, 109.6,
109.4, 105.21, 105.18, 83.2, 83.0, 80.1, 77.6, 77.3, 72.3, 71.9, 67.7, 67.4, 55.7 (q, J = 29.3 Hz), 55.6 (q,
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J = 28.9 Hz) 26.9, 26.83, 26.78, 26.3, 25.1, 24.9 ppm; F{1H} NMR (376 MHz, CDCl3) δ -70.6 (s,
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1.5F), -70.7 (s, 1.5F) ppm; HRMS-ESI m/z : [M+Cl]- calcd for C21H25ClF3O7 481.1246, found
481.1240.
(2R,3R,4S,5S,6R)-2-(Acetoxymethyl)-6-((3,3,3-trifluoro-2-phenylpropanoyl)oxy)tetrahydro-2H-
pyran-3,4,5-triyl triacetate (5r). The product (192.1 mg, 72% yield) was purified with silica gel
chromatography (petroleum ether/ethyl acetate = 4/1) as a yellow oil and as an inseparable mixture of
diastereoisomers (d. r. = 56:44); 1H NMR (400 MHz, CDCl3) δ 7.49 – 7.43 (m, 5H), 6.15 (dd, J = 13.7,
1.5 Hz, 1H), 5.32 – 5.13 (m, 3H), 4.45 (qd, J = 8.3, 4.0 Hz, 1H), 4.25 (dd, J = 12.4, 5.7 Hz, 0.44H), 4.11
(ddd, J = 17.4, 12.4, 3.5 Hz, 1H), 4.00 (ddd, J = 9.8, 5.6, 2.0 Hz, 0.44H), 3.85 (dd, J = 12.5, 2.1 Hz,
0.56H), 3.34 (ddd, J = 10.1, 4.7, 2.1 Hz, 0.56H), 2.07 (ddd, J = 26.4, 20.7, 2.9 Hz, 12H) ppm; 13C{1H}
NMR (101 MHz, CDCl3) δ 170.4, 170.3, 169.7, 169.6, 169.51, 169.47, 169.3, 163.5 (d, J = 2.7 Hz),
163.3 (d, J = 2.5 Hz), 129.54, 129.50, 129.4, 129.3, 129.2, 129.1, 128.7, 128.3, 123.4 (q, J = 280.3 Hz),
123.3 (q, J = 279.7 Hz), 91.9, 91.2, 71.2, 70.7, 68.5, 68.4, 67.7, 65.2, 64.7, 61.9, 61.5, 55.1 (q, J = 29.2
Hz), 55.0 (q, J = 29.4 Hz), 20.50, 20.45, 20.4 ppm; 19F{1H} NMR (376 MHz, CDCl3) δ -70.0 (s, 1.32F),
-70.5 (s, 1.68F) ppm; HRMS-ESI m/z : [M+Na]+ calcd for C23H25F3NaO11+ 557.1241, found 557.1248.
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