1571
X.-H. Li et al.
Paper
Synthesis
IR (film): 2956 (m), 2927 (w), 2871 (w), 1723 (s), 1396 (w), 1240 (m),
1135 (s), 917 cm–1 (w).
IR (film): 2959 (m), 1719 (s), 1451 (m), 1263 (m), 1115 (s), 972 (m),
801 (m), 700 cm–1 (s).
1H NMR (400 MHz, CDCl3): δ = 0.90 (d, J = 6.4 Hz, 3 H), 0.93 (d, J = 6.4
Hz, 3 H), 1.41–1.47 (m, 1 H), 1.73–1.93 (m, 6 H), 2.18 (dd, J = 13.6, 8.0
Hz, 1 H), 2.52 (dd, J = 13.6, 6.4 Hz, 1 H), 4.32–4.35 (m, 2 H), 5.09–5.15
(m, 2 H), 5.71–5.81 (m, 1 H).
13C NMR (100 MHz, CDCl3): δ = 21.0, 23.3, 24.6, 24.8, 28.5, 45.1, 45.4,
47.6, 70.1, 119.1, 133.4, 175.8.
1H NMR (400 MHz, CDCl3): δ = 1.45–1.49 (m, 1 H), 1.65–1.69 (m, 1 H),
1.84–1.87 (m, 2 H), 2.31–2.37 (m, 1 H), 2.68 (d, J = 13.2 Hz, 1 H), 2.86–
2.92 (m, 1 H), 3.32 (d, J = 13.6 Hz, 1 H), 3.92–3.94 (m, 1 H), 4.10–4.14
(m, 1 H), 6.18–6.21 (m, 1 H), 6.47 (d, J = 15.6 Hz, 1 H), 7.19–7.35 (m,
10 H).
13C NMR (100 MHz, CDCl3): δ = 21.2, 28.0, 44.4, 45.8, 48.1, 70.2, 124.7,
126.2, 126.9, 127.5, 128.4, 128.6, 130.4, 134.3, 136.9, 137.0, 175.5.
HRMS: m/z [M + NH4]+ calcd for C21H26NO2: 324.1958; found:
HRMS: m/z [M + H]+ calcd for C12H21O2: 197.1542; found: 197.1540.
324.1961.
3-Allyl-3-methyltetrahydro-2H-pyran-2-one (3d)
Yield: 27.4 mg (89%); colorless oil; [α]D26 +3.3 (c = 1.00 in CHCl3).
3-Cinnamyl-3-phenyltetrahydro-2H-pyran-2-one (3h)
Yield: 52.6 mg (90%); colorless oil; [α]D26 +85.8 (c = 0.98 in CHCl3).
Chiral GC: VARIAN CHIRASIL-DEXCB column, 30 m × 0.25 mm × 0.12
μm [carrier gas: N2, injector temperature: 250 °C, split ratio: 30, con-
stant column flow: 10 psi, column temperature 60 °C (5 min), 60–150
°C (3 °C/min), 150 °C (5 min), 150–180 °C (3 °C/min), FID detector
temperature: 250 °C], tR = 31.2 min, 31.5 min; ee = 92%.
HPLC: Chiralpak PC-2; hexane–i-PrOH (60/40), flow rate
mL/min, 230 nm, tR = 16.1 min, 17.1 min; ee = 54%.
= 0.5
IR (film): 2964 (m), 1714 (m), 1448 (w), 1262 (s), 1094 (s), 1023 (s),
802 cm–1 (s).
1H NMR (400 MHz, CDCl3): δ = 1.02–1.89 (m, 2 H), 2.03–2.12 (m, 1 H),
2.44–2.50 (m, 1 H), 2.63–2.69 (m, 1 H), 2.90–2.96 (m, 1 H), 3.97–4.00
(m, 1 H), 4.16–4.20 (m, 1 H), 6.06–6.10 (m, 1 H), 6.36 (d, J = 16.0 Hz, 1
H), 7.19–7.31 (m, 10 H).
HPLC: Chiralpak AD-H; i-PrOH–hexane (3:97), flow rate: 0.7 mL/min,
214 nm, tR (minor) = 12.8 min, tR (major) = 13.5 min; ee = 91%.
1H NMR (400 MHz, CDCl3): δ = 1.30 (s, 3 H), 1.57–1.66 (m, 1 H), 1.84–
1.97 (m, 3 H), 2.20 (dd, J = 13.6, 8.0 Hz, 1 H), 2.54 (dd, J = 13.2, 6.8 Hz,
1 H), 4.25–4.39 (m, 2 H), 5.10–5.16 (m, 2 H), 5.70–5.81 (m, 1 H).
13C NMR (100 MHz, CDCl3): δ = 20.6, 26.3, 31.6, 42.2, 44.5, 70.4, 102.5,
13C NMR (100 MHz, CDCl3): δ = 19.4, 27.9, 45.2, 51.7, 67.9, 125.4,
119.1, 133.2, 176.1.
126.0, 126.2, 127.3, 127.4, 128.5, 129.0, 133.9, 137.2, 140.4, 174.3.
HRMS: m/z [M + NH4]+ calcd for C20H24NO2: 310.1802; found:
310.1805.
3-Allyl-3-phenyltetrahydro-2H-pyran-2-one (3e)
Yield: 34.6 mg (80%); colorless oil; [α]D26 +81.4 (c = 0.99 in CHCl3).
(E)-3-[3-(Furan-2-yl)allyl]-3-phenyltetrahydro-2H-pyran-2-one
(3i)
HPLC: Chiralpak OJ-H; hexane–i-PrOH (90/10), flow rate
mL/min, 214 nm, tR = 18.3 min, 20.0 min; ee = 48%.
= 0.7
26
Yield: 49.6 mg (88%); slightly yellow oil; [α]D +62.2 (c = 0.99 in
IR (film): 2963 (w), 1729 (s), 1446 (w), 1261 (m), 1151 (m), 1094 (s),
798 (m), 701 cm–1 (m).
CHCl3).
HPLC: Chiralpak PC-2; hexane–i-PrOH (60/40), flow rate
mL/min, 230 nm, tR = 12.9 min, 14.1 min; ee = 59%.
= 0.5
1H NMR (400 MHz, CDCl3): δ = 1.69–1.88 (m, 1 H), 1.93–2.01 (m, 1 H),
2.33–2.39 (m, 1 H), 2.47 (dd, J = 13.6, 7.6 Hz, 1 H), 2.69 (dd, J = 13.6,
6.8 Hz, 1 H), 3.90–3.96 (m, 1 H), 4.09–4.15 (m, 1 H), 4.94–5.00 (m, 2
H), 5.54–5.65 (m, 1 H), 7.19–7.31 (m, 5 H).
IR (film): 2963 (m), 2906 (s), 1411 (s), 1259 (m), 1081 (s), 1014 (s),
794 (s), 701 cm–1 (m).
13C NMR (100 MHz, CDCl3): δ = 19.4, 27.9, 45.9, 51.1, 67.8, 118.8,
126.0, 127.3, 128.8, 133.7, 140.4, 174.2.
HRMS: m/z [M + H]+ calcd for C14H17O2: 217.1229; found: 217.1228.
1H NMR (400 MHz, CDCl3): δ = 1.80–1.92 (m, 2 H), 2.06–2.11 (m, 2 H),
2.44–2.50 (m, 1 H), 2.63 (dd, J = 14.0, 7.2 Hz, 1 H), 2.63 (dd, J = 14.0,
8.4 Hz, 1 H), 3.97–4.00 (m, 1 H), 4.16–4.23 (m, 1 H), 5.99–6.05 (m, 1
H), 6.13–6.21 (m, 2 H), 6.32–6.34 (m, 1 H), 7.29–7.40 (m, 5 H).
13C NMR (100 MHz, CDCl3): δ = 19.5, 27.9, 45.0, 51.7, 67.9, 106.9,
111.1, 122.4, 124.1, 126.0, 127.4, 129.0, 140.3, 141.6, 152.7, 174.2.
HRMS: m/z [M + NH4]+ calcd for C18H22NO3: 300.1594; found:
3-Allyl-3-methylchroman-2-one (3f)
26
Yield: 39.6 mg (98%); slightly yellow oil; [α]D –6.9 (c = 0.05 in
CHCl3).
300.1596.
HPLC: Chiralpak OJ-H; hexane–i-PrOH (95/5), flow rate = 0.5 mL/min,
214 nm, tR = 13.4 min, 14.5 min; ee = 94%.
3-Cinnamyl-3-methyltetrahydro-2H-pyran-2-one (3j)
Yield: 30.8 mg (67%); colorless oil; [α]D26 +0.58 (c = 1.07 in CHCl3).
1H NMR (400 MHz, CDCl3): δ = 1.26 (s, 3 H), 2.28–2.40 (m, 2 H), 2.75
(d, J = 16.0 Hz, 1 H), 2.91 (d, J = 16.0 Hz, 1 H), 5.03 (d, J = 16.8 Hz, 1 H),
5.14 (d, J = 10.4 Hz, 1 H), 5.73–5.84 (m, 1 H), 7.01 (d, J = 8.0 Hz, 1 H),
7.07 (d, J = 7.2 Hz, 1 H), 7.14 (d, J = 6.4 Hz, 1 H), 7.23–7.27 (m, 1 H).
HPLC: Chiralpak AD-H; i-PrOH–hexane (5:95); flow rate: 0.7 mL/min,
214 nm, tR = 15.7 min, 17.7 min; ee = 93%.
13C NMR (100 MHz, CDCl3): δ = 22.2, 35.4, 40.4, 40.8, 116.0, 119.6,
121.6, 124.3, 128.1, 128.5, 132.2, 151.2, 172.6.
HPLC: Chiralpak PC-2; hexane–i-PrOH (60/40), flow rate
mL/min, 230 nm, tR = 15.7 min, 17.7 min.
= 0.5
IR (film): 2962 (m), 1725 (w), 1258 (s), 1076 (s), 1011 (s), 789 cm–1
(m).
1H NMR (400 MHz, CDCl3): δ = 1.35 (s, 3 H), 1.64–1.68 (m, 1 H), 1.87–
1.99 (m, 3 H), 2.36 (dd, J = 14.0, 7.2 Hz, 1 H), 2.74 (dd, J = 13.6, 8.4 Hz,
1 H), 4.28–4.36 (m, 2 H), 6.15–6.18 (m, 1 H), 6.46 (d, J = 16.0 Hz, 1 H),
7.22–7.35 (m, 5 H).
3-Benzyl-3-cinnamyltetrahydro-2H-pyran-2-one (3g)
Yield: 47.7 mg (78%); colorless oil; [α]D26 –5.2 (c = 0.97 in CHCl3).
HPLC: Chiralpak PA-2; hexane–i-PrOH (95/5), flow rate = 0.7 mL/min,
214 nm, tR = 42.2 min, 46.3 min; ee = 87%.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 1568–1572