V. Mamane et al. / Tetrahedron 63 (2007) 5754–5767
5763
4.4.6. 6-Allyl-tetrahydropyran-2-one 11.37 From resin 10
(240 mg, 0.19 mmol) and DIpc2BAll (0.80 mmol) following
the general procedure and the cleavage method B, the lac-
tone (R)-11 was obtained (26 mg, 96%, er¼80:20). From
128.9 (2C), 132.0, 138.2, 178.5 ppm; IR (KBr): nmax¼3064,
3028, 2929, 1769 (C]O), 1496, 1355, 1160, 966, 921 cmꢀ1
;
MS (70 eV, EI) m/z (%): 216 (16) [M+], 175 (44) [M+ꢀallyl],
157 (28), 148 (62), 129 (39), 91 (100) [Bn]; MS (ESI) m/z
(%): 234 (100) [M++NH4], 217 (20) [M++1]; HRMS (EI)
calcd for C14H16O2: 216.1150, found 216.1131.
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resin 10 (315 mg, 0.25 mmol) and Ipc2BAll (1 mmol) fol-
lowing the general procedure and the cleavage method B,
the lactone (S)-11 was obtained (30 mg, 85%, er¼92:8) as
a colorless oil. (S)-11: [a]2D0 +30.1 (c 1.50, CHCl3),
4.4.10. (3R,5R)-5-Allyldihydro-3-methylfuran-2(3H)-one
15d. From resin 15d and Ipc2BAll following the general
1
L
Ref. 37 for (R)-11, [a]2D0 ꢀ32.4 (c 1.73, CHCl3); H NMR
(400 MHz, CDCl3): d¼1.56 (m, 1H), 1.80 (m, 1H), 1.90
(m, 2H), 2.35–2.60 (m, 4H), 4.35 (ddd, J¼17.0, 6.2,
2.7 Hz, 1H), 5.16 (m, 2H), 5.80 ppm (ddt, J¼17.2, 10.4,
7.0 Hz, 1H); MS (70 eV, EI) m/z (%): 99 (100)
[M+ꢀC3H5], 71 (70), 55 (30), 43 (32).
procedure and the cleavage method B, the lactone 15d
(50 mg, 87%, dr¼85:15, from 476 mg of 14f) was obtained
1
as a colorless oil. H NMR (400 MHz, CDCl3): d¼1.25 (d,
J¼7.2 Hz, 3H), 1.96 (dt, J¼12.9, 7.8 Hz, 1H), 2.16 (ddd,
J¼12.9, 9.2, 4.7 Hz, 1H), 2.30–2.39 (m, 1H), 2.40–2.50
(m, 1H), 2.67 (m, 1H), 4.55 (dtd, J¼9.4, 6.2, 4.7 Hz, 1H),
5.11–5.17 (m, 2H), 5.75 ppm (m, 1H); 13C NMR
(100 MHz, CDCl3): d¼15.8, 33.9, 34.4 (CH2), 39.3 (CH2),
77.4, 119.0 (CH2), 132.1, 180.1 ppm; IR (KBr): nmax¼2936,
1770, 1455, 1353, 1174, 921 cmꢀ1; MS (70 eV, EI) m/z (%):
99 (100) [M+ꢀallyl], 71 (34), 43 (38); HRMS (FAB,
m-NBA) m/z calcd for C8H12O2: 140.0837, found
141.0926 [M++H].
4.4.7. (3S,6R)-6-Allyl-3-benzyl-tetrahydropyran-2-one
15a. From resin 15a and Ipc2BAll following the general
D
procedure and the cleavage method B, the lactone 15a
(19 mg, 75%, dr¼86:14, from 143 mg of 14c) was obtained
as a colorless oil. 1H NMR (400 MHz, CDCl3): d¼1.46–1.67
(m, 2H), 1.79–1.92 (m, 2H), 2.25–2.37 (m, 1H), 2.38–2.48
(m, 1H), 2.62 (dd, J¼13.7, 4.3 Hz, 1H), 2.68–2.75 (m,
1H), 3.31 (dd, J¼13.7, 4.3 Hz, 1H), 4.30 (ddd, J¼16.8,
6.2, 3.5 Hz, 1H), 5.07–5.13 (m, 2H), 5.72–5.83 (ddt,
J¼17.0, 9.2, 7.0 Hz, 1H), 7.16–7.30 ppm (m, 5H); 13C
NMR/DEPT (100 MHz, CDCl3): d¼22.5 (CH2), 25.8
(CH2), 36.8 (CH2), 39.5 (CH2), 40.1, 77.4, 126.4 (CH2),
128.5 (2C), 129.1 (2C), 132.7, 139.0, 174.9 ppm; IR
(KBr): nmax¼2926, 1732 (C]O), 1644, 1538, 1454, 1383,
1184, 743 cmꢀ1; MS (70 eV, EI) m/z (%): 230 (21) [M+],
189 (15) [M+ꢀallyl], 117 (60), 91 (100) [Bn]; MS (ESI)
m/z (%): 230 (100) [M+]; HRMS (FAB, m-NBA) calcd for
C15H18O2: 230.1307, found 231.1358 [M++H].
4.4.11. (3S,5S)-5-Allyl-3-ethyldihydrofuran-2(3H)-one
15e. From resin 13e and Ipc2BAll following the general
D
procedure and the cleavage method B, the lactone 15e
(8 mg, 37%, dr¼87:13, from 153 mg of 14g) was obtained
1
as a colorless oil. H NMR (400 MHz, CDCl3): d¼0.98 (t,
J¼7.6 Hz, 3H), 1.45–1.57 (m, 1H), 1.78–1.88 (m, 1H),
1.97–2.14 (m, 2H), 2.30–2.39 (ap sext, J¼6.8 Hz, 1H),
2.40–2.48 (ap sext, J¼6.4 Hz, 1H), 2.49–2.57 (m, 1H),
4.53 (dddd, J¼12.6, 6.4, 6.2, 2.4 Hz, 1H), 5.11–5.18 (m,
2H), 5.71–5.81 ppm (ddt, J¼17.1, 7.0, 3.5 Hz, 1H); 13C
NMR (100 MHz, CDCl3): d¼11.6, 24.0, 32.1, 39.6, 40.1,
77.5, 118.9, 132.2, 179.1 ppm; IR (KBr): nmax¼3079,
4.4.8. (3S,6R)-6-Allyl-tetrahydro-3-methylpyran-2-one
15b. From resin 15b and Ipc2BAll following the general
L
2965, 1769 (C]O), 1643, 1463, 1355, 1177, 923 cmꢀ1
;
procedure and the cleavage method B, the lactone 15b
(42 mg, 85%, dr¼87:13, from 377 mg of 14d) was obtained
as a colorless oil. 1H NMR (400 MHz, CDCl3): d¼1.27 (d,
J¼6.8 Hz, 3H), 1.47–1.64 (m, 2H), 1.88–1.94 (m, 1H),
1.96–2.03 (m, 1H), 2.29–2.49 (m, 3H), 4.31 (ddd, J¼17.2,
6.1, 3.3 Hz, 1H), 5.08–5.14 (m, 2H), 5.79 ppm (ddt,
J¼17.2, 10.4, 7.0 Hz, 1H); 13C NMR/DEPT (100 MHz,
CDCl3): d¼17.3, 28.3 (CH2), 28.5 (CH2), 36.1, 40.4
(CH2), 80.9, 118.5 (CH2), 132.6, 174.2 ppm (CO); IR
(KBr): nmax¼2924, 2854, 1732 (C]O), 1463, 1378, 1177,
917 cmꢀ1; MS (70 eV, EI) m/z: 113 (100) [M+ꢀallyl], 85
(65), 67 (54), 41 (61) [allyl]; HRMS (EI) m/z calcd for
C9H14O2: 154.0994, found 154.1004.
MS (70 eV, EI) m/z (%): 113 (100) [M+ꢀallyl], 85 (25)
[M+ꢀallylꢀEt]; HRMS (EI) m/z C9H14O2: 154.0994, found
154.0985.
4.4.12. (3S,5R)-5-Allyl-3-butyldihydrofuran-2(3H)-one
15f. From resin 13f (839 mg) and Ipc2BAll (1.68 mmol)
L
following the general procedure and the cleavage method
B, the lactone 15f (79 mg, 51%, dr¼91:9) was obtained as
a colorless oil. [a]2D0 +29.50 (c 2.0, CHCl3); 1H NMR
(400 MHz, CDCl3): d¼0.90 (t, J¼7.2 Hz, 1H), 1.33 (m,
4H), 2.35–2.65 (m, 4H), 4.42 (ddd, J¼11.9, 10.2, 6.2 Hz,
1H), 5.13–5.18 (m, 2H), 5.76 ppm (ddt, J¼17.2, 10.2,
6.8 Hz, 1H); 13C NMR/DEPT (100 MHz, CDCl3): d¼13.8,
22.4 (CH2), 29.4 (CH2), 29.9 (CH2), 34.4 (CH2), 39.4
(CH2), 40.8, 77.6, 118.6 (CH2), 132.1, 178.7 ppm (CO); IR
(KBr): nmax¼3080, 2932, 1770 (C]O), 1644, 1455, 1353,
1174, 920 cmꢀ1; MS (70 eV, EI) m/z (%): 141 (100)
[M+ꢀallyl], 95 (20); HRMS (EI) m/z C11H18O2: 182.1307;
found 182.1315.
4.4.9. (3R,5R)-5-Allyl-3-benzyl-dihydrofuran-2(3H)-one
15c. From resin 15c and LIpc2BAll following the general pro-
cedure and the cleavage method B, the lactone 15c (50 mg,
60%, dr¼88:12, from 477 mg of 14e) was obtained as a
colorless oil. [a]D20 ꢀ19.67 (c 1.20, CHCl3); 1H NMR
(400 MHz, CDCl3): d¼1.95 (ddd, J¼14.2, 9.2, 5.1 Hz,
1H), 2.05 (dt, J¼15.4, 7.6 Hz, 1H), 2.24–2.32 (m, 1H),
2.36–2.43 (m, 1H), 2.76 (dd, J¼13.8, 9.3 Hz, 1H), 2.92
(dtd, J¼9.3, 7.4, 4.4 Hz, 1H), 3.16 (dd, J¼13.8, 4.4 Hz,
1H), 4.36 (ap quint, J¼6.2 Hz, 1H), 5.07–5.13 (m, 2H),
5.70 (ddt, J¼13.9, 9.6, 6.8 Hz, 1H), 7.15 (m, 2H), 7.23 (m,
1H), 7.28 ppm (m, 2H); 13C NMR (100 MHz, CDCl3):
d¼31.6, 36.5, 39.4, 40.9, 77.4, 118.9, 126.8, 128.7 (2C),
4.4.13. (3S,5R)-5-Allyldihydro-3-phenylethylfuran-
2(3H)-one 15g. From resin 13g (240 mg) and Ipc2BAll
L
(0.5 mmol) following the general procedure and the cleav-
age method B, the lactone 15g (35 mg, 66%, dr¼82:18)
was obtained as a colorless oil. 1H NMR (400 MHz,
CDCl3): d¼1.64 (dt, J¼12.1, 10.6 Hz, 1H), 1.75–1.85 (dtd,
J¼19.6, 9.0, 5.8 Hz, 1H), 2.28–2.37 (m, 1H), 2.44–2.50