8
C. Simon et al. / Tetrahedron xxx (2013) 1e10
65e67 ꢁC). IR nmax/cmꢀ1 3028, 2940, 2872, 1633, 1601, 1576, 1449,
4.15. General procedure for THP deprotection (GP-3): (E)-(4-
1349,1201,1183,1158,1108,1020,1005, 967, 946, 905, 807, 779, 712;
(3-methoxystyryl)-phenyl)methanol 5a
1H NMR (300 MHz, CDCl3)
d
7.42 (d, J¼8.1 Hz, 2H, CHAr), 7.29
(d, J¼8.1 Hz, 2H, CHAr), 7.22e7.07 (m, 3H includes AB system of
double bound), 7.01 (d, J¼2.0 Hz, 2H, CHAr), 6.89 (dd, J¼8.1, 2.0 Hz,
1H, CHAr), 5.40 (t, J¼3.3 Hz, 1H, ArOeCHeO) 4.72 (d, J¼12.0 Hz,
1H, AreCHHOeTHP), 4.65 (t, J¼3.3 Hz, 1H, OeCHeO), 4.44
(d, J¼12.0 Hz, 1H, AreCHHOeTHP), 3.91e3.83 (m, 2H,
CH2eHCHeCHO), 3.60e3.45 (m, 2H, CH2eHCHeCHO), 2.02e1.46
In a round bottom flask, THP protected alcohol 14a (1.32 g,
4.12 mmol, 1 equiv) and PPTS (104 mg, 0.41 mmol, 0.1 equiv) were
dissolved in ethanol (30 mL) at rt. The reaction mixture was heated
to 60 ꢁC for 6 h. The solvent was then removed under reduced
pressure to give a beige solid. Recrystallisation from petroleum
ether 60e80 ꢁC gave the title compound 5a (454 mg, 46%) as
a white solid (mp 85e87 ꢁC). IR nmax/cmꢀ1 3728, 2970, 1584; UV
lmax (MeOH)/nm 286.50 (ε dmꢀ3 molꢀ1 cmꢀ1 52,517); 1H NMR
(m, 12H, 6ꢃ CH2 (THP)); 13C NMR (75 MHz, CDCl3)
d 157.4 (C), 138.7
(C), 137.7 (C), 136.6 (C), 129.5 (HC]CH), 128.6 (HC]CH), 128.5
(CHAr), 128.2 (2ꢃ CHAr), 126.5 (2ꢃ CHAr), 120.1 (CHAr), 115.8 (CHAr),
114.3 (CHAr), 97.7 (ArOeCHeO), 96.3 (OeCHeO), 68.6 (AreCH2O),
62.1 (CH2O (THP)), 62.0 (CH2O (THP)), 30.6 (CH2), 30.4 (CH2), 25.5
(CH2), 25.2 (CH2), 19.47 (CH2), 18.7 (CH2).
(300 MHz, MeOD)
d
7.51 (d, J¼8.4 Hz, 2 H, CHAr), 7.33 (d, J¼8.1 Hz,
2H, CHAr), 7.24 (d, AB system, J¼16.0 Hz, trans CH]CH), 7.08e7.21
(m, 4H includes 1H AB system of double bound), 6.80 (dd, J¼2.1,
8.0 Hz, 1H, CHAr), 4.59 (s, 2H, CH2O), 3.81 (s, 3H, CH3O); 13C NMR
(75 MHz, MeOD)
d 211.5 (C), 142.2 (C), 140.3 (C), 137.9 (C), 130.7
(CHAr), 129.7 (CH]CH), 129.5 (CH]CH), 128.4 (2ꢃ CHAr), 127.6 (2ꢃ
CHAr), 120.8 (CHAr), 114.3 (CHAr), 112.8 (CHAr), 65.0 (CH2), 55.7
(CH3); m/z (EI) 240.11461 (Mþ C16H16O2 requires 240.11503). Elem.
Anal. Calcd. C, 80.08; H, 6.70. (C16H16O2 requires C, 79.97%; H,
6.71%.)
4.13. (E)-2,20-(5-(4-((Tetrahydro-2H-pyran-2-yloxy)methyl)
styryl)-1,3-phenylene)bis(oxy) bis(tetrahydro-2H-pyran) 14d
Compound 14d was synthesised according to the general pro-
cedure GP-2 from phosphonate 6 (2.24 g, 7.12 mmol, 1.05 equiv)
dissolved in dry DMF (12 mL), sodium methoxide (733 mg,
13.6 mmol, 2 equiv) and the aldehyde 7g (2.09 g, 6.78 mmol,
1 equiv) dissolved in DMF (12 mL). The title compound 14d (2.58 g,
73%) was obtained after work-up and purification by column
chromatography (hexane/ethyl acetated85:15/80:20) as a pale
4.16. (E)-(4-(3,5-Dimethoxystyryl)phenyl)methanol 5b
Compound 5b was synthesised according to the general pro-
cedure GP-3 from THP protected alcohol 14b (724 mg, 2.04 mmol,
1 equiv) dissolved in ethanol (15 mL) and PPTS (63 mg, 0.25 mmol,
0.12 equiv). The title compound 5b (243 mg, 44%) was obtained
after work-up and recrystallisation from petroleum ether 60e80 ꢁC
as a white solid (mp 77e80 ꢁC). IR nmax/cmꢀ1 3346, 2835, 1585,
yellow oil. 1H NMR (300 MHz, CDCl3)
d
7.48 (d, J¼8.3 Hz, 2H, CHAr),
7.35 (d, J¼8.3 Hz, 2H, CHAr), 7.10 and 7.00 (2ꢃ d, AB system,
J¼16.4 Hz, CH]CH), 6.89 (t, J¼1.8 Hz, 2H, CHAr), 6.71 (dd, J¼3.3,
2.0 Hz, 1H, CHAr), 5.46 (t, J¼3.3 Hz, 2H, ArOeCHeO), 4.79 (d,
J¼12.0 Hz, 1H, AreCHHOeTHP), 4.72 (t, J¼3.3 Hz, 1H, OeCHeO),
4.51 (d, J¼12.0 Hz, 1H, AreCHHOeTHP), 3.98e3.90 (m, 3H,
CH2eHCHeCHO), 3.66e3.52 (m, 3H, CH2eHCHeCHO), 2.10e1.53
1455; 1H NMR (300 MHz, MeOD)
d
7.50 (d, J¼8.4 Hz, 2H, CHAr), 7.33
(d, J¼8.4 Hz, 2H, CHAr), 7.06 and 7.11 (2ꢃ d, AB system, J¼16.1 Hz,
trans CH]CH), 6.69 (d, J¼2.1 Hz, 2H, CHAr), 6.38 (t, J¼2.1 Hz, 1H,
CHAr), 4.59 (s, 2H, CH2O), 3.79 (s, 6H, 2ꢃ CH3O); 13C (300 MHz,
(m, 18H, 9ꢃ CH2 (THP)); 13C NMR (75 MHz, CDCl3)
d 158.3 (C), 158.2
MeOD)
d
162.5 (2ꢃ C), 142.2 (CIV), 140.9 (CIV), 137.9 (CIV), 129.9
(C), 139.1 (C), 137.7 (C), 136.5 (C), 128.7 (HC]CH), 128.6 (HC]CH),
128.1 (2ꢃ CHAr), 126.5 (2ꢃ CHAr), 108.0 (CHAr), 107.9 (CHAr), 104.8
(CH), 97.7 (OeCHeO), 96.4 (ArOeCHeO), 96.2 (ArOeCHeO), 68.5
(AreCH2O), 62.1 (CH2O (THP)), 61.9 (CH2O (THP)), 61.9 (CH2O
(THP)), 30.6 (CH2), 30.3 (2ꢃ CH2), 25.5 (CH2), 25.2 (2ꢃ CH2), 19.3
(CH2), 18.7 (CH2), 18.6 (CH2).
(CH]CH), 129.6 (CH]CH), 128.4 (2ꢃ CHAr), 127.7 (2ꢃ CHAr), 105.6
(CHAr), 100.9 (CHAr), 65.0 (CH2), 55.8 (2ꢃ CH3); m/z (EI) 270.12522
(Mþ C17H18O3 requires 270.12559). Elem. Anal. Calcd. C, 75.53; H,
6.71. (C17H18O3 requires C, 75.66%; H, 6.60%.)
4.17. (E)-(4-(3-Hydroxystyryl)phenyl)methanol 5c
4.14. (E)-2,20-(5-(4-((Tetrahydro-2H-pyran-2-yloxy)methyl)
styryl)-1,3-phenylene)bis (methylene)bis(oxy)bis(tetrahydro-
2H-pyran) 14e
Compound 5c was synthesised according to the general pro-
cedure GP-3 from THP protected alcohol 14c (706 mg, 1.79 mmol,
1 equiv) dissolved in ethanol (20 mL) and PPTS (127 mg, 0.51 mmol,
0.29 equiv). The title compound 5c (210 mg, 52%) was obtained
after work-up and recrystallisation from petroleum ether 60e80 ꢁC
as a white solid (mp >200 ꢁC). IR nmax/cmꢀ1 3394, 3137, 1588, 1445;
Compound 14e was synthesised according to the general pro-
cedure GP-2 from phosphonate 6 (896 mg, 2.85 mmol, 1.13 equiv)
dissolved in dry DMF (4 mL), sodium methoxide (292 mg,
5.4 mmol, 2.13 equiv) and the aldehyde 7h (846 mg, 2.53 mmol,
1 equiv) dissolved in DMF (4 mL). The title compound 14e (1.06 g,
80%) was obtained after work-up and purification by column
chromatography (hexane/ethyl acetated85:15/80:20) as a pale
1H (300 MHz, MeOD)
d
7.49 (d, J¼8.1 Hz, 2H, CHAr), 7.33 (d, J¼8.1 Hz,
2H, CHAr), 6.99 and 7.03 (2ꢃ d, AB system, J¼16.2 Hz, 2ꢃ 1H, trans
CH]CH), 6.49 (d, J¼2.1 Hz, 2H, CHAr), 6.20 (t, J¼2.0 Hz, 2H, CHAr),
4.60 (s, 2H, CH2O); 13C (300 MHz, MeOD)
d
159.8 (2ꢃ C), 142.1 (C),
140.9 (C), 137.9 (C), 129.8 (CH]CH), 129.2 (CH]CH), 128.4 (2ꢃ
CHAr),127.5 (2ꢃ CHAr),106.1 (2ꢃ CHAr),103.2 (CHAr), 65.0 (CH2); m/z
(EI) 225.0920 ([MꢀH]ꢀ C15H13Oꢀ2 requires 225.0921).
yellow oil. 1H NMR (300 MHz, CDCl3)
d
7.42 (d, J¼8.1 Hz, 2H, CHAr),
7.37 (s, 2H, CHAr), 7.28 (d, J¼8.1 Hz, 2H, CHAr), 7.19 (s, 1H, CHAr),
7.05 and 7.04 (2ꢃ d, AB system, J¼16.8 Hz, CH]CH), 4.74
(d, J¼12.0 Hz, 2H, AreCHHOeTHP), 4.72 (d, J¼12.0 Hz, 1H,
AreCHHOeTHP), 4.66 (t, J¼3.9 Hz, 3H, OeCHeO), 4.46 (d,
J¼12.0 Hz, 1H, AreCHHOeTHP), 4.44 (d, J¼12.0 Hz, 1H,
AreCHHOeTHP), 3.91e3.82 (m, 3H, CH2eHCHeCHO), 3.53e3.45
(m, 3H, CH2eHCHeCHO), 1.84e1.46 (m, 18H, 6ꢃ CH2 (THP)); 13C
4.18. (E)-(5-(4-Hydroxymethyl)styryl)benzene-1,3-diol 5d
Compound 5d was synthesised according to the general pro-
cedure GP-3 from THP protected alcohol 14d (724 mg, 2.04 mmol,
1 equiv) dissolved in ethanol (15 mL) and PPTS (63 mg, 0.25 mmol,
0.12 equiv). The title compound 5d (243 mg, 44%) was obtained
after work-up and recrystallisation from petroleum ether 60e80 ꢁC
as a white solid (mp >220 ꢁC). IR nmax/cmꢀ1 3223, 2970, 1584; 1H
NMR (75 MHz, CDCl3)
d
138.8 (2ꢃ C), 137.7 (C), 137.6 (C), 136.6 (C),
128.7 (HC]CH), 128.4 (HC]CH), 128.2 (2ꢃ CHAr), 126.6 (CHAr),
126.5 (2ꢃ CHAr), 125.1 (2ꢃ CHAr), 97.8 (2ꢃ CHO), 97.7 (CHO), 68.7
(2ꢃ CH2O), 68.5 (CHO), 62.2 (2ꢃ CH2O), 62.1 (CH2O), 30.6
(3ꢃ CH2), 25.5 (3ꢃ CH2), 19.4 (3ꢃ CH2); m/z (FAB) 522.
NMR (300 MHz, MeOD)
(d, J¼8.1 Hz, 2H, CHAr), 6.99 and 7.03 (2ꢃ d, AB system, J¼16.2 Hz,
d
7.49 (d, J¼8.1 Hz, 2H, CHAr), 7.33