3
358
A. Aponick, B. Biannic
PRACTICAL SYNTHETIC PROCEDURES
IR (neat): 3418, 2937, 2863, 2741, 1683, 1635, 1134, 1060, 977
cm .
TLC analysis indicated a complete reaction and the mixture filtered
through a short plug of silica with CH Cl (4 mL). The solution of
–
1
2
2
1
crude product was concentrated in vacuo, and purified by flash
chromatography (5% EtOAc–hexanes) to give 83.8 mg (92%) of
H NMR (300 MHz, CDCl ): d = 9.49 (d, J = 7.8 Hz, 1 H), 6.87 (dt,
3
J = 15.6, 6.6 Hz, 1 H), 6.13 (ddt, J = 15.6, 7.8, 1.8 Hz, 1 H), 3.68 (t,
J = 6.2 Hz, 2 H), 2.43–2.35 (m, 2 H), 2.01 (br, 1 H), 1.67–1.59 (m,
4
the title compound 17 as a colorless oil; R = 0.95 (50% EtOAc–
f
hexanes);
H).
1
3
IR (neat): 3418, 2937, 2863, 2741, 1683, 1635, 1134, 1060, 977
cm .
C NMR (75 MHz, CDCl ): d = 194.4, 159.1, 133.0, 62.1, 32.4,
3
–1
3
2.0, 24.1.
1H NMR (300 MHz, CDCl
.30 (dd, J = 15.3, 6.3 Hz, 1 H), 4.95 (d, J = 11.4 Hz, 1 H), 3.69 (t,
J = 8.4 Hz, 1 H), 3.43 (t, J = 11.1 Hz, 1 H), 1.81–1.34 (m, 8 H),
): d = 5.61 (dt, J = 15.3, 7.8 Hz, 1 H),
+
3
HRMS (ESI): m/z calcd for C H NO (M + NH ) : 146.1176;
found: 146.1165.
7
16
2
4
5
–
0.03 (s, 9 H).
(
E)-Tridec-5-ene-1,7-diol (4)
1
3
A solution of n-hexylmagnesium bromide (0.97 M in Et O, 34.02
C NMR (75 MHz, CDCl ): d = 130.2, 128.5, 78.9, 69.46, 32.8,
2
3
mL, 2.2 equiv) was added in a dropwise fashion to a solution of 3
26.1, 23.7, 22.9, –1.8.
(
1.9225 g, 15.0 mmol) in THF (75 mL) at 0 °C. The mixture was
+
HRMS (ESI): m/z calcd for C H OSi (M + H) : 199.1513; found:
1
1
23
stirred 30 min at the same temperature and then quenched with aq
sat. NH Cl (50 mL), diluted with H O (100 mL), and extracted with
1
99.1525.
4
2
EtOAc (3 × 80 mL). The combined organic layers were dried
(
(
E)-2-[4-(1,3-Dioxolan-2-yl)but-1-enyl]tetrahydro-2H-pyran
14)
(
MgSO ), concentrated, and the residue was purified by flash chro-
4
matography (40% EtOAc–hexanes) to give 2.8244 g (88%) of the
Colorless oil; R = 0.92 (50% EtOAc–hexanes).
f
title compound as a yellow oil: R = 0.33 (50% EtOAc–hexanes).
f
–
1
IR (neat): 2935, 2850, 1808, 1083, 1048 cm .
–
1
IR (neat): 3346, 2929, 2857, 1457, 1058, 968 cm .
1
H NMR (300 MHz, CDCl ): d = 5.61 (ddt, J = 15.3, 7.4, 1.5, Hz, 1
1
3
H NMR (300 MHz, CDCl ): d = 5.62 (dt, J = 15.6, 6.3 Hz, 1 H),
3
H), 5.43 (ddt, J = 15.3, 6.0, 0.9 Hz, 1 H), 4.80 (t, J = 4.8 Hz, 1 H),
5
.45 (dd, J = 15.6, 6.9 Hz, 1 H), 4.02 (q, J = 6.3 Hz, 1 H), 3.63 (t,
3
.95–3.64 (m, 5 H), 3.40 (dt, J = 11.7, 3.3 Hz, 2 H), 2.10 (q, J = 7.4
J = 6.0 Hz, 2 H), 2.06 (q, J = 6.9 Hz, 2 H), 1.94 (br, 1 H), 1.60–1.23
Hz, 2 H), 1.79–1.18 (m, 8 H).
1
(
m, 14 H), 0.88 (t, J = 7.2 Hz, 3 H).
3
C NMR (75 MHz, CDCl ): d = 132.0, 130.8, 104.3, 78.3, 68.5,
1
3
3
C NMR (75 MHz, CDCl ): d = 133.7, 131.6, 73.3, 62.8, 37.5, 32.3,
3
6
5.1, 33.5, 32.4, 27.0, 26.1, 23.6.
3
2.0, 32.0, 29.4, 25.6, 25.5, 22.8, 14.2;
+
HRMS (ESI): m/z calcd for C H O (M + H) : 213.1485; found:
2
+
12 21
3
HRMS (ESI): m/z calcd for C H (M + H – 2H O) : 179.1794;
1
3
23
2
13.1482.
found: 179.1790.
(
E)-2-[2-(Furan-2-yl)vinyl]tetrahydro-2H-pyran (15)
(
E)-2-(Oct-1-enyl)tetrahydro-2H-pyran (5)
Yellow oil; R = 0.95 (50% EtOAc–hexanes).
f
Anhyd CH Cl (25 mL, degassed by bubbling with argon for 30
min) was added to an aluminum foil covered, flame dried, 100 mL
flask containing Ph PAuCl (24.8 mg, 0.05 mmol, 0.5 mol%),
AgOTf (12.8 mg, 0.05 mmol, 0.5 mol%), and activated 4 Å MS
2
2
–
1
IR (neat): 2937, 2848, 1726, 1083, 1013 cm .
1
3
H NMR (300 MHz, CDCl ): d = 7.32 (d, J = 1.8 Hz, 1 H), 6.41 (dd,
3
J = 16.2, 1.5 Hz, 1 H), 6.34 (dd, J = 3.9, 1.8 Hz, 1 H), 6.21 (d,
J = 3.3 Hz, 1 H), 6.15 (dd, J = 16.2, 5.4 Hz, 1 H), 3.46 (dt, J = 11.7,
(
950 mg). The heterogeneous mixture was vigorously stirred for 10
min and a solution of the diol 4 (2.1432 g, 10.0 mmol) in anhyd
CH Cl (25 mL, degassed by bubbling with argon for 30 min) was
2
.7 Hz, 1 H), 4.08–4.03 (m, 1 H), 3.94 (ddt, J = 10.8, 5.4, 1.8 Hz, 1
2
2
H), 3.52 (dt, J = 11.4, 3.0 Hz, 1 H), 1.90–1.41 (m, 6 H).
1
then added. After 5 h, TLC analysis indicated a complete reaction
and the mixture filtered through a short plug of silica with CH Cl
3
C NMR (75 MHz, CDCl ): d = 152.9, 141.9, 129.7, 118.1, 111.4,
3
2
2
1
07.9, 77.6, 68.6, 32.4, 26.1, 23.7.
(
30 mL). The solution of crude product was concentrated in vacuo,
and purified by flash chromatography (5% EtOAc–hexanes) to give
.7944 g (91%) of the title compound as a colorless oil; R = 0.95
+
HRMS (ESI): m/z calcd for C11
178.0994.
H
O
(M) : 178.0984; found:
14
2
1
f
(
5% EtOAc–hexanes).
–
1
(E)-2-[2-(Cyanomethyl)vinyl]tetrahydro-2H-pyran (16)
IR (neat): 2927, 2854, 2728, 1463, 1086, 967 cm .
Pale yellow oil; R = 0.78 (5% EtOAc–hexanes).
f
1
H NMR (300 MHz, CDCl ): d = 5.65 (ddt, J = 15.6, 6.6, 0.9 Hz, 1
3
IR (neat): 2920, 2849, 2732, 2251, 1723, 1119, 1083 cm–1.
H), 5.44 (ddt, J = 15.6, 6.3, 1.5 Hz, 1 H), 4.01–3.95 (m, 1 H), 3.75–
1H NMR (300 MHz, CDCl
): d = 5.88 (ddt, J = 15.6, 5.1, 1.5 Hz, 1
3
2
.70 (m, 1 H), 3.46 (dt, J = 11.4, 1.5 Hz, 1 H), 2.00 (q, J = 6.3 Hz,
H), 1.85–1.22 (m, 14 H), 0.86 (t, J = 6.3 Hz, 3 H).
3
H), 5.61 (ddt, J = 15.6, 5.4, 1.5 Hz, 1 H), 4.04–3.99 (m, 1 H), 3.85–
3.79 (m, 1 H), 3.48 (dt, J = 5.4, 2.7 Hz, 1 H), 3.11 (dt, J = 11.4, 1.5
Hz, 2 H), 1.89–1.25 (m, 6 H).
1
3
C NMR (75 MHz, CDCl ): d = 132.1, 131.3, 78.5, 68.5, 32.5, 32.4,
3
3
1.9, 29.3, 29.1, 26.1, 23.6, 22.8, 14.2.
13C NMR (75 MHz, CDCl
2.0, 25.9, 23.5, 20.5.
): d = 136.7, 117.9, 117.5, 76.9, 68.6,
+
3
HRMS (ESI): m/z calcd for C H O (M + H) : 197.1891; found:
1
1
3
25
3
97.1900.
+
HRMS (ESI): m/z calcd for C H NO (M + H) : 152.1075; found:
9
14
Representative Procedure for Small Scale Reactions
E)-Trimethyl[3-(tetrahydro-2H-pyran-2-yl)allyl]silane (17)
Anhyd CH Cl (1.6 mL) was added to an aluminum foil covered,
152.1072.
(
(E)-2-(3-Phenylprop-1-enyl)tetrahydro-2H-pyran (18)
Colorless oil; R = 0.95 (50% EtOAc–hexanes).
2
2
flame dried, test tube containing Ph PAuCl (2.3 mg, 0.0046 mmol,
f
3
1
4
.0 mol%), AgOTf (1.2 mg, 0.0046 mmol, 1.0 mol%), and activated
Å MS (30 mg). The heterogeneous mixture was vigorously stirred
IR (neat): 3026, 2934, 2843, 1495, 1452, 1085, 698 cm–1.
1
H NMR (300 MHz, CDCl ): d = 7.30–7.16 (m, 5 H), 5.82 (dt,
for 10 min and a solution of the corresponding diol (100.2 mg, 0.46
mmol) in anhyd CH Cl (1.6 mL) was then added. After 40 min,
3
J = 15.3, 6.9 Hz, 1 H), 5.53 (dd, J = 15.3 6.3 Hz, 1 H), 3.99 (dt,
2
2
Synthesis 2008, No. 20, 3356–3359 © Thieme Stuttgart · New York