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doi.org/10.1002/ejoc.202000846
EurJOC
European Journal of Organic Chemistry
(300 MHz, CDCl3): δ = 7.70 (s, 1H), 7.60 (d, J = 15.0 Hz, 1H), 7.39 (d,
J = 8.3 Hz, 2H), 6.76 (d, J = 15.3 Hz, 1H), 6.64–6.56 (m, 2H), 5.90–
5.84 (m, 1H), 5.15 (t, J = 3.3 Hz, 1H), 4.45 (m, J = 19.4, 6.7 Hz, 2H),
4.13–4.03 (m, 1H), 2.96 (s, 6H), 1.99 (m, 9H). 13C NMR (75 MHz,
CDCl3): δ = 185.4, 169.3, 168.6, 168.4, 154.3, 150.1, 143.3, 129.2,
121.5, 114.3, 113.0, 110.8, 73.7, 65.3, 61.4, 60.0, 39.1, 19.8, 19.7, 19.6.
IR (ν, cm–1) = 2861, 2829, 2712, 1689, 1574, 1559, 1527, 1475, 1186,
1145, 996, 791. HRMS (ESI-TOF) calcd. [C23H27NO8Na+] 468.1629,
found 468.1629. [α]20D = –115.5 (0.84, CHCl3).
2756, 1689, 1572, 1553, 1445, 1326, 1184, 1153, 996. HRMS (ESI-
TOF) calcd. [C21H21ClO8Na+] 459.0817, found 459.0829. [α]20
=
D
–39.5 (0.20, CHCl3).
(E)-1-((2R,3S,4R)-3,4-Bis(benzyloxy)-2-((benzyloxy)methyl)-3,4-
dihydro-2H-pyran-5-yl)-3-(naphthalen-2-yl)prop-2-en-1-one
(3j): Compound 3j was synthesized according to General Procedure
B and obtained as a yellow oil (48.3 mg, 0.081 mmol, 54 %). 1H NMR
(300 MHz, CDCl3): δ = 7.82–7.70 (m, 1H), 7.64 (s, 1H), 7.42–7.10 (m,
23H), 4.64–4.57 (m, 2H), 4.49 (s, 1H), 4.45 (d, J = 5.3 Hz, 1H), 4.41 (s,
2H), 4.36 (s, 1H), 4.31 (q, J = 3.3, 2.3 Hz, 1H), 3.75 (t, J = 2.3 Hz, 1H),
3.68 (dd, J = 10.7, 7.6 Hz, 1H), 3.55 (dd, J = 10.6, 5.0 Hz, 1H). 13C
NMR (75 MHz, CDCl3): δ = 183.4, 158.6, 138.0, 137.7, 137.3, 128.6,
128.5, 128.4, 128.3, 128.2, 128.1, 128.1, 128.0, 127.9, 127.9, 127.8,
127.8, 127.8, 127.8, 126.2, 125.9, 125.9, 125.4, 125.2, 121.3, 117.8,
117.8, 79.0, 73.4, 72.6, 71.6, 71.3, 68.2, 67.6. IR (ν, cm–1) = 2964,
2930, 2820, 1710, 1650, 1598, 1570, 1523, 1462, 1156, 1037, 998.
HRMS (ESI-TOF) calcd. [C40H36O5Na+] 619.2455, found 619.2459.
[α]20D = –20.2 (0.55, CHCl3).
(2R,3S,4S)-2-(Acetoxymethyl)-5-((E)-3-(p-tolyl)acryloyl)-3,4-di-
hydro-2H-pyran-3,4-diyl Diacetate (3e): Compound 3e was syn-
thesized according to General Procedure B and obtained as a yellow
oil (40.6 mg, 0.097 mmol, 65 %). 1H NMR (300 MHz, CDCl3): δ = 7.81
(s, 1H), 7.68 (d, J = 15.4 Hz, 1H), 7.46 (d, J = 7.9 Hz, 2H), 7.20 (d, J =
7.7 Hz, 2H), 7.00 (d, J = 15.4 Hz, 1H), 5.98–5.81 (m, 1H), 5.24 (d, J =
2.9 Hz, 1H), 4.68–4.39 (m, 2H), 4.29–4.02 (m, 1H), 2.38 (s, 3H), 2.20–
1.92 (m, 9H). 13C NMR (75 MHz, CDCl3): δ = 186.4, 170.3, 169.5,
169.3, 156.3, 143.5, 140.9, 132.0, 129.7, 128.3, 119.5, 114.0, 74.9, 66.1,
62.1, 60.9, 21.5, 20.8, 20.7, 20.6. IR (ν, cm–1) = 2857, 2827, 2760,
1685, 1601, 1572, 1546, 1464, 1324, 1179, 1143, 991, 788. HRMS (ESI-
TOF) calcd. [C22H24O8Na+] 439.1363, found 439.1369. [α]20D = –30.5
(0.21, CHCl3).
(E)-1-((2R,3S,4R)-3,4-Bis(benzyloxy)-2-((benzyloxy)methyl)-3,4-
dihydro-2H-pyran-5-yl)-3-phenylprop-2-en-1-one (3k): Com-
pound 3k was synthesized according to General Procedure B in a
0.5 mmol scale and was obtained as a yellow oil (145 mg,
0.265 mmol, 53 %). 1H NMR (300 MHz, CDCl3): δ = 7.88 (s, 1H), 7.76
(d, J = 15.6 Hz, 1H), 7.61 (dd, J = 6.8, 2.9 Hz, 2H), 7.52–7.25 (m, 18H),
7.17 (d, J = 15.6 Hz, 1H), 4.78–4.53 (m, 8H), 3.97–3.88 (m, 2H), 3.74
(dd, J = 10.8, 4.6 Hz, 1H). 13C NMR (75 MHz, CDCl3): δ = 188.4, 156.5,
142.3, 138.4, 137.8, 137.5, 135.1, 130.1, 128.9, 128.6, 128.5, 128.4,
128.2, 128.1, 128.1, 127.9, 127.9, 127.8, 127.8, 121.4, 116.2, 77.7, 73.4,
72.6, 71.6, 71.5, 68.5, 66.9. IR (ν, cm–1) = 3030, 2968, 2934, 2814,
1710, 1654, 1580, 1568, 1520, 1458, 1156, 1132, 1052, 1032, 996.
HRMS (ESI-TOF) calcd. [C36H34O5Na+] 569.2298, found 569.2296.
[α]20D = –37.0 (0.05, CHCl3). Spectroscopic data are consistent with
those previously reported.[18]
(2R,3S,4R)-2-(Acetoxymethyl)-5-((E)-3-(naphthalen-2-yl)acryl-
oyl)-3,4-dihydro-2H-pyran-3,4-diyl Diacetate (3f): Compound 3f
was synthesized according to General Procedure B and obtained as
a yellow solid (40.7 mg, 0.09 mmol, 60 %). 1H NMR (300 MHz, CDCl3):
δ = 7.90 (s, 1H), 7.84–7.71 (m, 5H), 7.62 (d, J = 8.7 Hz, 1H), 7.51–
7.36 (m, 2H), 7.08 (d, J = 15.5 Hz, 1H), 5.87 (dd, J = 3.3, 1.6 Hz, 1H),
5.18 (d, J = 3.2 Hz, 1H), 4.60–4.31 (m, 2H), 4.13 (dd, J = 11.7, 3.9 Hz,
1H), 2.11–1.92 (m, 9H). 13C NMR (75 MHz, CDCl3): δ = 185.3, 169.3,
168.5, 168.2, 155.4, 142.5, 133.3, 132.3, 131.2, 129.3, 127.7, 127.5,
126.7, 126.3, 125.7, 122.5, 119.6, 113.1, 73.9, 65.1, 61.0, 59.9, 19.7,
19.7, 19.6. IR (ν, cm–1) = 2859, 2827, 2773, 2758, 1685, 1601, 1572,
1540, 1460, 1324, 1179, 1149, 992, 951, 728. HRMS (ESI-TOF) calcd.
[C25H24O8Na+] 475.1363, found 475.1365. [α]20D = –29.4 (0.17,
CHCl3).
(E)-1-((2R,3S,4R)-3,4-Bis(benzyloxy)-2-((benzyloxy)methyl)-3,4-
dihydro-2H-pyran-5-yl)-3-(4-methoxyphenyl)prop-2-en-1-one
(3l): Compound 3l was synthesized according to General Procedure
B in a 0.5 mmol scale and was obtained as a yellow oil (164 mg,
0.285 mmol, 57 %). 1H NMR (300 MHz, CDCl3): δ = 7.84 (s, 1H), 7.72
(d, J = 15.4 Hz, 1H), 7.54 (d, J = 8.7 Hz, 1H), 7.39–7.30 (m, 15H), 7.04
(d, J = 15.5 Hz, 1H), 6.94 (d, J = 8.8 Hz, 2H), 4.77–4.49 (m, 8H), 3.96–
3.90 (m, 2H), 3.84 (s, 2H), 3.72 (dd, J = 10.7, 4.4 Hz, 1H). 13C NMR
(75 MHz, CDCl3): δ = 188.4, 161.3, 156.1, 142.1, 138.4, 137.9, 137.6,
129.9, 128.6, 128.5, 128.4, 128.1, 128.0, 127.9, 127.8, 127.8, 127.8,
127.7, 119.1, 116.2, 114.4, 77.6, 73.4, 72.5, 71.6, 71.5, 68.5, 67.0, 55.4
IR (ν, cm–1) = 2985, 2943, 2841, 1716, 1658, 1568, 1508, 1438, 1165,
1001, 996. HRMS (ESI-TOF) calcd. [C37H36O6Na+] 599.2404, found
599.2406. [α]20D = –40.0 (0.23, CHCl3).
(2R,3S,4S)-2-(Acetoxymethyl)-5-cinnamoyl-3,4-dihydro-2H-
pyran-3,4-diyl Diacetate (3g): 3g was synthesized according to
General Procedure B in a 0.5 mmol scale and was obtained as a
yellow oil (131 mg, 0.325 mmol, 65 %). 1H NMR (300 MHz, CDCl3):
δ 7.81 (s, 1H), 7.64 (d, J = 15.5 Hz, 1H), 7.51 (dd, J = 6.7, 3.0 Hz, 2H),
7.39–7.29 (m, 3H), 7.03 (d, J = 15.6 Hz, 1H), 5.87 (dd, J = 3.1, 1.6 Hz,
1H), 5.19 (t, J = 3.1 Hz, 1H), 4.63–4.54 (m, 1H), 4.48 (dd, J = 11.9,
7.9 Hz, 1H), 4.15 (dd, J = 11.9, 4.0 Hz, 1H), 2.08–1.99 (m, 9H). 13C
NMR (75 MHz, CDCl3): δ = 186.4, 170.3, 169.5, 169.3, 156.6, 143.3,
134.7, 130.4, 128.9, 128.3, 120.5, 114.1, 74.9, 66.1, 62.0, 60.9, 20.7,
20.7, 20.6. IR (ν, cm–1) = 2859, 2829, 1685, 1601, 1572, 1542, 1404,
1324, 1272, 1177, 1149, 992, 950, 881, 851, 743, 617, 567. HRMS (ESI-
TOF) calcd. [C21H22O8Na+] 425.1207, found 425.1222. [α]20D = –30.2
(0.25, CHCl3). Spectroscopic data are consistent with those previ-
ously reported.[18]
(3R,4R)-5-((E)-3-(4-Methoxyphenyl)acryloyl)-3,4-dihydro-2H-
pyran-3,4-diyl Diacetate (4a): Compound 4a was synthesized ac-
cording to General Procedure B and obtained as a yellow solid
(48.1 mg, 0.133 mmol, 89 %). 1H NMR (300 MHz, CDCl3): δ = 7.92 (s,
1H), 7.68 (d, J = 15.4 Hz, 1H), 7.52 (d, J = 8.6 Hz, 2H), 7.04–6.86 (m,
3H), 5.86 (d, J = 2.4 Hz, 1H), 5.04 (d, J = 2.3 Hz, 1H), 4.52–4.39 (m,
1H), 4.07 (d, J = 12.5 Hz, 1H), 3.84 (d, J = 0.8 Hz, 3H), 2.07 (s, 6H).
13C NMR (75 MHz, CDCl3): δ = 186.7, 169.6, 169.3, 161.5, 158.5, 143.0,
130.0, 127.6, 118.1, 114.4, 113.6, 65.5, 64.5, 60.7, 55.4, 21.0, 20.8.
IR (ν, cm–1) = 2857, 2829, 2747, 1680, 1596, 1568, 1538, 1521, 1462,
1326, 1179, 1156, 1136, 992, 802, 780. HRMS (ESI-TOF) calcd.
[C19H20O7Na+] 383.1101, found 383.1111. [α]20D = –137.0 (0.05,
CHCl3).
(2R,3S,4R)-2-(Acetoxymethyl)-5-((E)-3-(4-chlorophenyl)acryloyl)-
3,4-dihydro-2H-pyran-3,4-diyl Diacetate (3h): Compound 3h was
synthesized according to General Procedure B in a 0.5 mmol scale
and was obtained as a yellow oil (135 mg, 0.310 mmol, 62 %).
1H NMR (300 MHz, CDCl3): δ = 7.81 (s, 1H), 7.61 (d, J = 15.7 Hz, 1H),
7.47 (d, J = 8.5 Hz, 2H), 7.34 (d, J = 8.2 Hz, 2H), 7.01 (d, J = 15.5 Hz,
1H), 5.88 (d, J = 3.1 Hz, 1H), 5.21 (d, J = 3.2 Hz, 1H), 4.59 (q, J =
3.8 Hz, 1H), 4.51 (dd, J = 11.9, 7.9 Hz, 1H), 4.16 (dd, J = 11.9, 3.9 Hz,
1H), 2.10–1.99 (m, 9H). 13C NMR (75 MHz, CDCl3): δ = 186.1, 170.3,
169.5, 169.3, 156.6, 141.9, 136.3, 133.2, 129.4, 129.2, 121.0, 114.0, (3R,4R)-5-((E)-3-(p-Tolyl)acryloyl)-3,4-dihydro-2H-pyran-3,4-diyl
75.00, 66.1, 61.9, 60.9, 20.7, 20.7, 20.6. IR (ν, cm–1) = 2857, 2827, Diacetate (4b): Compound 4b was synthesized according to Gen-
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