6446
A. Ida et al. / Tetrahedron 71 (2015) 6442e6448
1
6
36.2, 135.9,128.5,128.5, 128.3, 128.3, 127.7, 126.4,126.1, 125.9, 73.2,
24 2
264 (24), 191 (34), 159 (base); HRMS (EI): Calcd for C20H O m/z
296.1776, found 296.1779; >99% ee, [HPLC conditions: column
Daicel OD-H, eluent 1% 2-propanol in hexane, flow rate 0.5 mL/min,
þ
3.5, 40.2, 31.7, 26.1,18.4, ꢀ4.1, ꢀ4.6; LRMS (FAB) m/z 405 (MþNa) ;
þ
HRMS (FAB) Calcd for C24
H
34
O
2
SiNa (MþNa) 405.2226, found
405.2229; >99% ee, [HPLC conditions: column Daicel OD-H, eluent
1% 2-propanol in hexane, flow rate 1.0 mL/min, wavelength
254 nm, t (R)¼24 min].
(S)¼16 min, t
wavelength 254 nm, t
r
(S)¼21 min, t
r
(R)¼39 min].
r
r
3.2.8. (S,E)-3-Mehoxy[5-(2-methoxymethyl)phenyl]-1-phenyl-pent-
2
4
1
-ene (þ)-4e. Colorless oil; Rf¼0.35 (10% EtOAc in hexane); [
a]
D
1
3.2.4. (S,E)-3-tert-Butyldimethylsilyloxy-5-[(2-hydroxymethyl)-phe-
þ2.3 (c 0.40, CHCl
3 3
); H NMR (400 MHz, CDCl ) d 7.42e7.40 (2H, m),
nyl]-1-phenylpent-1-ene (ꢀ)-4b. Colorless oil; Rf¼0.40 (20% EtOAc
7.37e7.31 (3H, m), 7.28e7.17 (4H, m), 6.56 (1H, d, J¼15.9 Hz), 6.10
(1H, dd, J¼15.9, 7.9 Hz), 4.48 (2H, s), 3.74 (1H, q, J¼7.9 Hz), 3.38 (3H,
2
0
ꢀ1
1
in hexane); [
a]
D
ꢀ22.6 (c 0.40, EtOH); IR (CHCl
7.38e7.36 (3H, m), 7.34e7.30 (2H, t,
3
, cm ): 3349; H
1
3
NMR (400 MHz, CDCl
3
)
d
s), 3.35 (3H, s), 2.85e2.70 (2H, m), 1.99 (1H, m), 1.86 (1H, m);
C
J¼10.0 Hz), 7.25e7.18(4H, m), 6.54 (1H, d, J¼16.2 Hz), 6.21 (1H, dd,
3
NMR (100 MHz, CDCl ) d 140.6, 136.6, 135.7, 132.5, 130.0, 129.4,
J¼16.2, 6.4 Hz), 4.73 (2H, d, J¼5.0 Hz), 4.39 (1H, q, J¼6.4 Hz), 2.84
129.1, 128.6, 128.0, 127.7, 126.5, 125.9, 81.8, 72.6, 58.2, 56.2, 37.0,
þ
(
(
1H, m), 2.72 (1H, m), 1.91e1.86 (2H, m), 1.68 (1H, t, J¼5.9 Hz), 0.95
28.0; LRMS (EI): m/z (rel. int. %) 296 (M , 0.9), 264 (28), 159 (20),
13
9H, s), 0.11 (3H, s), 0.08 (3H, s); C NMR (100 MHz, CDCl
3
)
d
140.5,
24 2
147 (base); HRMS (EI): Calcd for C20H O m/z 296.1776, found
1
38.3, 137.0, 132.8, 129.5, 129.3, 128.6, 128.3, 128.0, 127.4, 126.4,
296.1773; >99% ee, [HPLC conditions: column Daicel AD-H column,
eluent 1% 2-propanol in hexane, flow rate 0.5 mL/min, wavelength
126.2, 73.4, 63.1, 39.9, 27.9, 25.9, 18.3, ꢀ4.2, ꢀ4.7; LRMS (FAB) m/z
4
4
þ
þ
05 (MþNa) ; HRMS (FAB) Calcd for C24
H
34
O
2
SiNa (MþNa)
254 nm, t
r
(R)¼24 min, t (S)¼34 min].
r
05.2226, found 405.2229; >99% ee, [HPLC conditions: column
Daicel AD-H, eluent 1% 2-propanol in hexane, flow rate 1.0 mL/min,
wavelength 254 nm, t (S)¼27 min].
(R)¼23 min, t
3.2.9. (R)-3-Methoxy[2-(2-methoxymethyl)phenyl]-1-phenyl-pent-
0
23
r
r
1-ene (ꢀ)-3e . Colorless oil; Rf¼0.45 (10% EtOAc in hexane); [
a]
D
1
ꢀ
5.8 (c 0.65, CHCl
3
); H NMR (400 MHz, CDCl
3
)
d
7.45 (1H, dd,
3
.2.5. (R,E)-3-tert-Butyldimethylsilyloxy-1-(2-methylphenyl)-5-
J¼6.9, 1.6 Hz), 7.31e7.21 (5H, m), 7.17e7.08 (3H, m), 5.46 (1H, dd,
J¼2.0, 1.3 Hz), 5.14 (1H, dd, J¼2.0, 0.4 Hz), 4.45 (1H, d, J¼11.4 Hz),
4.39 (1H, d, J¼11.4 Hz), 3.82 (1H, m), 3.48 (3H, s), 3.35 (3H, s), 2.80
(1H, ddd, J¼13.7, 10.2, 5.0 Hz), 2.59 (1H, ddd, J¼13.7, 10.0, 6.5 Hz),
phenylpent-1-ene (3c) and (S,E)-3-tert-butyldimethylsilyloxy-5-(2-
methylphenyl)-1-phenylpent-1-ene (4c). A mixture of 3c and 4c.
1
Colorless oil; Rf¼0.33 (2.5% EtOAc in hexane); H NMR (400 MHz,
13
CDCl
3
)
d
7.45e7.11 (9H, m, 3cþ4c), 6.78 (0.62H, dd, J¼15.7, 1.0 Hz,
3
1.79 (1H, m), 1.68 (1H, m); C NMR (100 MHz, CDCl ) d 146.6, 142.0,
3
4
2
c), 6.57 (0.38H, d, J¼15.9 Hz, 4c), 6.26 (0.38H, dd, J¼15.9, 6.4 Hz,
c), 6.12 (0.62H, dd, J¼15.7, 6.3 Hz, 3c), 4.41e4.36 (1H, m, 3cþ4c),
.81e2.65 (2H, m, 3cþ4c), 2.37 (1.86H, s, 3c), 2.33 (1.14H, s, 4c),
139.9, 135.6, 129.1, 128.9, 128.4, 128.3, 127.3, 127.3, 125.7, 115.7, 84.1
þ
72.3, 58.1, 57.0, 36.0, 31.9; LRMS (EI): m/z (rel. int. %) 296 (M , 13),
264 (10), 232 (9), 173 (base); HRMS (EI): Calcd for C20
24 2
H O m/z
1.98e1.84 (2H, m, 3cþ4c), 0.98 (3.42H, s, 4c), 0.97 (5.58H, s, 3c), 0.14
296.1776, found 296.1769.
13
(1.14H, s, 4c), 0.13 (1.86H, s, 3c), 0.10 (3H, s, 3cþ4c); C NMR
(100 MHz, CDCl 142.4 (3c), 140.6 (4c), 137.1 (4c), 136.3 (3c), 135.9
(4c),135.4 (3c),134.4 (3c),133.0 (4c),130.2,130.1,129.3,128.7,128.5,
28.4, 128.3, 127.4, 127.3, 127.2, 126.4, 126.1 (4c), 125.9 (4c), 125.8,
25.7, 125.7, 73.4 (4c), 73.1 (3c), 40.1 (3c), 38.9 (4c), 31.5 (3c), 29.0
3
)
d
3.2.10. (E)-3-tert-Butyldimethylsilyloxy-1-[(2-hydroxymethyl)-phe-
nyl]-6-phenylhex-1-ene (3f). Colorless oil; Rf¼0.26 (10% EtOAc in
ꢀ1
1
1
1
hexane); IR (neat, cm ) 3337; H NMR (400 MHz, CDCl ) d 7.44
3
(1H, dd, J¼7.5, 1.9 Hz), 7.34 (1H, dd, J¼6.9, 2.0 Hz), 7.28e7.23 (4H,
m), 7.17e7.14 (3H, m), 6.79 (1H, dd, J¼15.6, 0.9 Hz), 6.08 (1H, dd,
J¼15.6, 6.3 Hz), 4.71 (2H, d, J¼3.9 Hz), 4.31 (1H, dtd, J¼6.3, 5.9,
(
4c), 25.9 (3c), 25.9 (4c), 19.9 (3c), 19.2 (4c), 18.3 (3c), 18.3 (4c), ꢀ4.2
(3c), ꢀ4.2 (4c), ꢀ4.7 (3c), ꢀ4.7 (4c).
0
.9 Hz), 2.62 (2H, dd, J¼7.8, 7.1 Hz), 1.80e1.53 (4H, m), 0.91 (9H, s),
13
3
.2.6. (R,E)-3-tert-Butyldimethylsilyloxy-1-(4-methylphenyl)-5-
3
0.07 (3H, s), 0.05 (3H, s); C NMR (100 MHz, CDCl ) d 142.4, 137.5,
phenylpent-1-ene (3d) and (S,E)-3-tert-butyldimethylsilyloxy-5-(4-
methylphenyl)-1-phenylpent-1-ene (4d). A mixture of 3d and 4d.
Colorless oil; Rf¼0.33 (2.5% EtOAc in hexane); H NMR (400 MHz,
136.1, 136.0, 128.4, 128.3, 128.2, 128.1, 127.5, 126.2, 125.7, 125.6, 73.3,
63.4, 37.9, 35.9, 26.9, 25.9, 18.2, ꢀ4.3, ꢀ4.7; LRMS (FAB) m/z 419
1
þ
(MþNa) ; HRMS (FAB) Calcd for C25
36 2
H O SiNa m/z 419.2382, found
CDCl
3
)
d
7.39e7.09 (9H, m, 3dþ4d), 6.53 (0.38H, dd, J¼15.9, 2.6 Hz,
419.2378.
4
2
3
d), 6.47 (0.62H, d, J¼15.8 Hz, 3d), 6.20 (0.38H, ddd, J¼15.9, 6.5,
.5 Hz, 4d), 6.15 (0.62H, dd, J¼15.8, 6.7 Hz, 3d), 4.36e4.29 (1H, m,
dþ4d), 2.75e2.63 (2H, m, 3dþ4d), 2.34 (1.86H, s, 3d), 2.32 (1.14H,
3.2.11. (E)-4-tert-Butyldimethylsilyloxy-6-[(2-hydroxymethyl)-phe-
nyl]-1-phenylhex-1-ene (4f). Colorless oil; Rf¼0.26 (10% EtOAc in
ꢀ
1
1
s, 4d), 1.96e1.83 (2H, m, 3dþ4d), 0.94 (3.42H, s, 4d), 0.93 (5.58H, s,
3
hexane); IR (neat, cm ) 3389; H NMR (400 MHz, CDCl )
3
d), 0.09 (1.86H, s, 3d), 0.09 (1.14H, s, 4d), 0.06 (1.14H, s, 4d), 0.05
1.86H, s, 3d); 13C NMR (100 MHz, CDCl
142.4 (3d), 142.4 (4d),
39.3 (4d), 137.2 (3d), 137.1 (4d), 135.1 (4d), 134.3 (3d), 133.1 (4d),
33.1 (3d), 132.1 (3d), 129.3, 129.2, 129.0, 128.5, 128.4, 128.3, 128.3,
d
7.37e7.17 (9H, m), 6.41 (1H, dd, J¼15.8, 1.2 Hz), 6.23 (1H, dt,
(
1
1
3
)
d
J¼15.8, 7.2 Hz), 4.71 (2H, d, J¼1.2 Hz), 3.90 (1H, m), 2.84 (1H, ddd,
J¼13.7, 11.3, 5.5 Hz), 2.67 (1H, ddd, J¼13.7, 11.5, 5.4 Hz), 2.44 (2H,
ddd, J¼7.2, 5.9, 1.2 Hz), 1.90e1.70 (2H, m), 0.94 (9H, s), 0.10 (3H, s),
13
1
4
28.2, 127.4, 127.3, 126.4, 126.3, 125.7, 125.7, 73.2 (3d), 73.1 (4d),
0.2 (4d), 40.1 (3d), 31.6 (3d), 31.1 (4d), 25.9 (3d), 25.9 (4d), 21.2
3
0.10 (3H, s); C NMR (100 MHz, CDCl ) d 140.7, 138.2, 137.6, 132.2,
129.3, 128.5, 128.3, 128.0, 127.0, 126.8, 126.2, 126.0, 72.1, 63.1, 41.0,
þ
(
ꢀ
3d), 21.0 (4d), 18.3 (3d), 18.3 (4d), ꢀ4.1 (4d), ꢀ4.2 (3d), ꢀ4.7 (3d),
38.6, 28.1, 25.9, 18.1, ꢀ4.3, ꢀ4.5; LRMS (FAB) m/z 419 (MþNa) ;
4.7 (4d).
HRMS (FAB) Calcd for C25
36
H O
2
SiNa (MþNa)þ m/z 419.2382, found
419.2388.
3
1
.2.7. (R,E)-3-Methoxy[1-(2-methoxymethyl)phenyl]-5-phenyl-pent-
2
3
-ene (ꢀ)-3e. Colorless oil; Rf¼0.35 (10% EtOAc in hexane); [
a
]
D
3.2.12. (E)-3-tert-Butyldimethylsilyloxy-1-[(2-hydroxymethyl)-phe-
1
ꢀ
9.5 (c 1.00, CHCl
3
); H NMR (400 MHz, CDCl
3
)
d
7.52 (1H, dd, J¼7.5,
nyl]-7-phenylhept-1-ene (3g). Colorless oil; Rf¼0.47 (20% EtOAc in
ꢀ1
1
1
.5 Hz), 7.37e7.18 (8H, m), 6.84 (1H, d, J¼15.7 Hz), 5.98 (1H, dd,
3
hexane); IR (neat, cm ) 3390; H NMR (400 MHz, CDCl ) d 7.46
J¼15.7, 7.9 Hz), 4.54 (1H, d, J¼11.7 Hz), 4.51 (1H, d, J¼11.7 Hz), 3.73
(1H, dd, J¼7.1, 1.8 Hz), 7.37 (1H, dd, J¼7.2, 2.0 Hz), 7.31e7.24 (4H, m),
7.19e7.15 (3H, m), 6.80 (1H, d, J¼15.7 Hz), 6.10 (1H, dd, J¼15.7,
6.3 Hz), 4.74 (2H, s), 4.29 (1H, dt, J¼6.3, 5.7 Hz), 2.62 (2H, dd, J¼8.0,
(
(
1H, q, J¼7.9 Hz), 3.40 (3H, s), 3.36 (3H, s), 2.78e2.73 (2H, m), 2.05
1H, m), 1.90 (1H, m); 1 C NMR (100 MHz, CDCl
3
) d 142.0, 136.1,
3
13
134.9,132.3,129.7,129.3,128.5,128.3,128.2,127.5,126.2,125.8, 81.6,
7.3 Hz), 1.69e1.39 (6H, m), 0.92 (9H, s), 0.08 (3H, s), 0.07 (3H, s);
C
þ
72.8, 58.1, 56.2, 37.2, 31.6; LRMS (EI): m/z (rel. int. %) 296 (M , 2),
3
NMR (100 MHz, CDCl ) d 142.6, 137.5, 136.3, 136.1, 128.4, 128.2,