The Journal of Organic Chemistry
Article
3H). 13C {1H} NMR (100 MHz, CDCl3): δ 199.3, 147.5, 125.6, 92.8,
88.7, 40.5, 37.8, 30.2, 25.1, 24.4. HRMS (ESI-TOF) m/z: [M + Na]+
calcd for C10H14O3Na, 205.0835; found, 205.0834.
2-Allyl-6-hydroxy-2H-pyran-3(6H)-one (2n). Isolation by column
chromatography over silica gel (eluent, 10:1 petroleum ether/ethyl
acetate) afforded 2n as a white solid (26 mg, 70% yield, 0.2 mmol of
1n as the starting material was used). Rf = 0.3 (5:1 petroleum ether/
2-Hydroxy-1-oxaspiro[5.7]tridec-3-en-5-one (2i). Isolation by
column chromatography over silica gel (eluent, 10:1 petroleum
ether/ethyl acetate) afforded 2i as a colorless oil (29 mg, 68% yield,
0.2 mmol of 1i as the starting material was used). Rf = 0.3 (5:1
petroleum ether/ethyl acetate). 1H NMR (400 MHz, CDCl3): δ 6.84
(dd, J = 10.3, 2.0 Hz, 1H), 6.02 (dd, J = 10.2, 1.4 Hz, 1H), 5.70−5.67
(m, 1H), 3.60 (d, J = 7.1 Hz, 1H), 2.15−2.07 (m, 1H), 1.98−1.85 (m,
3H), 1.79−1.69 (m, 2H), 1.63−1.51 (m, 8H). 13C {1H} NMR (100
MHz, CDCl3): δ 199.4, 145.3, 126.5, 87.6, 83.2, 33.0, 29.8, 28.0, 27.6,
24.3, 21.0, 20.8. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C12H18O3Na, 233.1148; found, 233.1158.
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ethyl acetate). H NMR (400 MHz, CDCl3) Major isomer: δ 6.91
(dd, J = 10.2, 3.5 Hz, 1H), 6.11 (d, J = 10.0 Hz, 1H), 5.86−5.75 (m,
1H), 5.65 (s, 1H), 5.02 (ddd, J = 17.1, 3.5, 1.7 Hz, 1H), 4.99−4.94
(m, 1H), 4.58 (dd, J = 8.0, 3.9 Hz, 1H), 3.51 (d, J = 4.5 Hz, 1H),
2.13−2.04 (m, 2H), 1.99−1.90 (m, 2H), 1.84−1.68 (m, 1H), 1.59−
1.48 (m, 1H). Minor isomer: δ 6.94 (dd, J = 10.1, 1.4 Hz, 1H), 6.15
(dd, J = 10.2, 1.6 Hz, 1H), 5.86−5.75 (m, 1H), 5.65 (s, 1H), 5.02
(ddd, J = 17.1, 3.5, 1.7 Hz, 1H), 4.99−4.94 (m, 1H), 4.09 (ddd, J =
8.3, 3.9, 1.1 Hz, 1H), 3.79 (d, J = 7.2 Hz, 1H), 2.13−2.04 (m, 2H),
1.99−1.90 (m, 2H), 1.84−1.68 (m, 1H), 1.59−1.48 (m, 1H). 13C
{1H} NMR (100 MHz, CDCl3) Major isomer: δ 196.7, 144.5, 138.3,
127.5, 114.8, 87.6, 74.0, 33.4, 29.0, 24.1. Minor isomer: δ 196.3,
147.9, 138.2, 128.7, 114.8, 90.8, 78.7, 33.4, 30.0, 24.3. HRMS (ESI-
TOF) m/z: [M + Na]+ calcd for C10H14O3Na, 205.0835; found,
205.0837.
6-Hydroxy-2-methyl-2-phenyl-2H-pyran-3(6H)-one (2j). Isolation
by column chromatography over silica gel (eluent, 10:1 petroleum
ether/ethyl acetate) afforded 2j as a colorless oil (27 mg, 67% yield,
0.2 mmol of 1j as the starting material was used). Rf = 0.3 (5:1
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petroleum ether/ethyl acetate). H NMR (400 MHz, CDCl3) Major
isomer: δ 7.39−7.29 (m, 5H), 6.80 (dd, J = 10.2, 1.3 Hz, 1H), 6.21
(dd, J = 10.2, 1.8 Hz, 1H), 5.43 (s, 1H), 3.86 (s, 1H), 1.66 (s, 3H).
Minor isomer: δ 7.39−7.29 (m, 5H), 6.90 (dd, J = 10.3, 2.5 Hz, 1H),
6.21 (dd, J = 10.2, 1.8 Hz, 1H), 5.77 (s, 1H), 3.86 (s, 1H), 1.71 (s,
3H). 13C {1H} NMR (100 MHz, CDCl3) Major isomer: δ 196.3,
147.6, 128.7, 128.3, 128.2, 125.3, 88.4, 83.4, 27.6, 26.0. Minor isomer:
δ 196.3, 145.7, 138.2, 128.3, 128.0, 126.8, 125.7, 88.3, 81.8, 26.0.
HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C12H12O3Na, 227.0679;
found, 227.0687.
6-Hydroxy-6-methyl-2-(prop-2-yn-1-yl)-2H-pyran-3(6H)-one
(2o). Isolation by column chromatography over silica gel (eluent, 10:1
petroleum ether/ethyl acetate) afforded 2o as a colorless oil (23 mg,
70% yield, 0.2 mmol of 1o as the starting material was used). Rf = 0.3
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(5:1 petroleum ether/ethyl acetate). H NMR (400 MHz, CDCl3)
Major isomer: δ 6.86 (d, J = 10.3 Hz, 1H), 6.06 (d, J = 10.2 Hz, 1H),
4.69 (dd, J = 7.5, 3.8 Hz, 1H), 3.19 (s, 1H), 2.86 (ddd, J = 17.3, 3.7,
2.8 Hz, 1H), 2.61 (ddd, J = 17.3, 7.6, 2.7 Hz, 1H), 2.01 (t, J = 2.6 Hz,
1H), 1.69 (s, 3H). Minor isomer: δ 6.92 (d, J = 10.4 Hz, 1H), 6.09 (d,
J = 10.3 Hz, 1H), 4.38 (dd, J = 6.9, 4.7 Hz, 1H), 3.58 (s, 1H), 2.86
(ddd, J = 17.3, 3.7, 2.8 Hz, 1H), 2.83−2.79 (m, 1H), 2.11 (t, J = 2.7
Hz, 1H), 1.65 (s, 3H). 13C {1H} NMR (100 MHz, CDCl3) Major
isomer: δ 194.7, 148.4, 126.1, 93.2, 80.4, 72.8, 69.7, 28.8, 20.1. Minor
isomer: δ 194.3, 150.5, 125.8, 94.0, 80.3, 76.1, 71.0, 25.6, 22.7. HRMS
(ESI-TOF) m/z: [M + Na]+ calcd for C9H10O3Na, 189.0522; found,
189.0522.
6-Hydroxy-2,2-diphenyl-2H-pyran-3(6H)-one (2k). Isolation by
column chromatography over silica gel (eluent, 8:1 petroleum ether/
ethyl acetate) afforded 2k as a colorless oil (30 mg, 56% yield, 0.2
mmol of 1k as the starting material was used). Rf = 0.4 (5:1 petroleum
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ether/ethyl acetate). H NMR (400 MHz, CDCl3): δ 7.39−7.26 (m,
10H), 6.89 (dd, J = 10.2, 1.4 Hz, 1H), 6.30 (dd, J = 10.3, 1.6 Hz, 1H),
5.49 (d, J = 4.3 Hz, 1H), 3.23 (d, J = 7.0 Hz, 1H). 13C {1H} NMR
(100 MHz, CDCl3): δ 194.2, 147.3, 141.3, 137.4, 129.0, 128.6, 128.6,
127.9, 127.7, 127.6, 127.5, 88.9, 86.9. HRMS (ESI-TOF) m/z: [M +
Na]+ calcd for C17H14O3Na, 289.0835; found, 289.0842.
2-Cyclopropyl-6-hydroxy-6-methyl-2H-pyran-3(6H)-one (2p).
Isolation by column chromatography over silica gel (eluent, 10:1
petroleum ether/ethyl acetate) afforded 2p as a yellowish oil (25 mg,
74% yield, 0.2 mmol of 1p as the starting material was used). Rf = 0.3
Ethyl-2-(6-hydroxy-6-methyl-3-oxo-3,6-dihydro-2H-pyran-2-yl)-
acetate (2l). Isolation by column chromatography over silica gel
(eluent, 8:1 petroleum ether/ethyl acetate) afforded 2l as a yellowish
oil (35 mg, 82% yield, 0.2 mmol of 1l as the starting material was
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(5:1 petroleum ether/ethyl acetate). H NMR (400 MHz, CDCl3)
Major isomer: δ 6.82 (d, J = 10.1 Hz, 1H), 6.03 (d, J = 10.1 Hz, 1H),
3.98 (d, J = 7.6 Hz, 1H), 3.70 (s, 1H), 1.64 (s, 3H), 1.21−1.14 (m,
1H), 0.74−0.67 (m, 1H), 0.55−0.44 (m, 2H), 0.39−0.33 (m, 1H).
Minor isomer: δ 6.89 (d, J = 10.4 Hz, 1H), 6.06 (d, J = 10.3 Hz, 1H),
3.70 (s, 1H), 3.51 (d, J = 8.4 Hz, 1H), 1.60 (s, 3H), 1.21−1.14 (m,
1H), 0.74−0.67 (m, 1H), 0.61−0.57 (m, 1H), 0.55−0.44 (m, 2H).
13C {1H} NMR (100 MHz, CDCl3) Major isomer: δ 196.7, 148.1,
126.2, 92.9, 77.2, 28.7, 10.9, 2.7, 1.1. Minor isomer: δ195.9, 149.9,
125.7, 93.8, 81.7, 28.6, 13.8, 3.5, 2.4. HRMS (ESI-TOF) m/z: [M +
Na]+ calcd for C9H12O3Na, 191.0679; found, 191.0681.
6-Hydroxy-5-oxaspiro[3.5]non-7-en-9-one (2q). Isolation by
column chromatography over silica gel (eluent, 10:1 petroleum
ether/ethyl acetate) afforded 2q as a yellowish oil (24 mg, 77% yield,
0.2 mmol of 1q as the starting material was used). Rf = 0.3 (5:1
petroleum ether/ethyl acetate). 1H NMR (400 MHz, CDCl3): δ 6.89
(dd, J = 10.2, 2.4 Hz, 1H), 6.11 (dd, J = 10.2, 1.0 Hz, 1H), 5.66 (d, J
= 3.8 Hz, 1H), 4.01 (d, J = 6.5 Hz, 1H), 2.60−2.52 (m, 1H), 2.48−
2.40 (m, 1H), 2.40−2.22 (m, 2H), 1.95−1.86 (m, 2H). 13C {1H}
NMR (100 MHz, CDCl3): δ 197.2, 145.6, 126.7, 88.1, 80.1, 34.1,
31.0, 13.6. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C8H10O3Na,
177.0522; found, 177.0526.
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used). Rf = 0.3 (5:1 petroleum ether/ethyl acetate). H NMR (400
MHz, CDCl3) Major isomer: δ 6.84 (d, J = 10.2 Hz, 1H), 6.05 (d, J =
10.2 Hz, 1H), 4.97 (dd, J = 7.6, 4.0 Hz, 1H), 4.19−4.12 (m, 2H), 3.80
(s, 1H), 2.99 (dd, J = 16.8, 4.0 Hz, 1H), 2.70 (dd, J = 16.8, 7.6 Hz,
1H), 1.62 (s, 3H), 1.26 (t, J = 7.1 Hz, 3H). Minor isomer: δ 6.91 (d, J
= 10.3 Hz, 1H), 6.09 (d, J = 10.3 Hz, 1H), 4.61 (dd, J = 6.5, 5.0 Hz,
1H), 4.19−4.12 (m, 2H), 4.04 (s, 1H), 2.92 (d, J = 0.9 Hz, 1H), 2.91
(d, J = 2.8 Hz, 1H), 1.62 (s, 3H), 1.26 (t, J = 7.1 Hz, 3H). 13C {1H}
NMR (100 MHz, CDCl3) Major isomer: δ 195.2, 171.0, 148.3, 125.9,
93.0, 71.2, 60.9, 35.2, 28.5, 14.1. Minor isomer: δ195.2, 171.0, 150.9,
125.8, 94.5, 74.4, 61.1, 37.0, 24.4, 14.1. HRMS (ESI-TOF) m/z: [M +
Na]+ calcd for C10H14O5Na, 237.0733; found, 237.0732.
6-Hydroxy-6-methyl-2-(2-methylallyl)-2H-pyran-3(6H)-one (2m).
Isolation by column chromatography over silica gel (eluent, 10:1
petroleum ether/ethyl acetate) afforded 2m as a colorless oil (27 mg,
74% yield, 0.2 mmol of 1m as the starting material was used). Rf = 0.4
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(5:1 petroleum ether/ethyl acetate). H NMR (400 MHz, CDCl3)
Major isomer: δ 6.82 (d, J = 10.1 Hz, 1H), 6.03 (d, J = 10.1 Hz, 1H),
4.82 (dd, J = 2.5, 1.0 Hz, 2H), 4.70 (dd, J = 9.2, 3.2 Hz, 1H), 3.18 (s,
1H), 2.78−2.72 (m, 1H), 2.35−2.27 (m, 1H), 1.77 (s, 3H), 1.63 (s,
3H). Minor isomer: δ 6.88 (d, J = 10.2 Hz, 1H), 6.06 (d, J = 10.2 Hz,
1H), 4.87 (s, 2H), 4.38 (dd, J = 9.9, 3.8 Hz, 1H), 3.25 (s, 1H), 2.64
(d, J = 3.7 Hz, 1H), 2.53 (dd, J = 15.1, 10.2 Hz, 1H), 1.78 (s, 3H),
1.61 (s, 3H). 13C {1H} NMR (100 MHz, CDCl3) Major isomer: δ
196.4, 147.9, 141.7, 126.3, 112.4, 92.8, 73.0, 37.0, 28.8, 22.9. Minor
isomer: δ 196.1, 150.1, 141.7, 125.9, 113.1, 94.1, 76.4, 39.6, 25.3, 22.2.
HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C10H14O3Na, 205.0835;
found, 205.0833.
(2s,4s)-6-Hydroxy-6-methyl-2-phenyl-5-oxaspiro[3.5]non-7-en-
9-one (2r). Isolation by column chromatography over silica gel
(eluent, 8:1 petroleum ether/ethyl acetate) afforded 2r as a white
solid (43 mg, 89% yield, 0.2 mmol of 1r as the starting material was
used). mp 98.1−98.9 °C. Rf = 0.3 (4:1 petroleum ether/ethyl
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acetate). H NMR (400 MHz, CDCl3) Major isomer: δ 7.32−7.17
(m, 5H), 6.84 (dd, J = 10.2, 2.9 Hz, 1H), 6.07 (dd, J = 10.2, 5.0 Hz,
1H), 3.51−3.39 (m, 1H), 3.19 (s, 1H), 3.06−2.97 (m, 1H), 2.93−
2.83 (m, 1H), 2.62−2.53 (m, 1H), 2.34−2.26 (m, 1H), 1.61 (s, 3H).
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J. Org. Chem. 2021, 86, 9563−9586