Tetraols as Templates for the Synthesis of Functionalized Macrocycles
02,10.04,8.012,16]octadecane (19b): General procedure F, boronic acid
1b (34.3 mg, 108 μmol) and anti-tetraol 11 (12.2 mg, 53.9 μmol) in
dry methanol (3 mL) and dry toluene (1.5 mL). Raw yield: 43.7 mg.
C
56H80B2O8 + Na+, calcd. 925.5950; found 925.5954 (Δ =
0.4 ppm); C5513C H80B2O8 + Na+, calcd. 926.5976; found 926.5969
(Δ = –0.8 ppm).
IR (ATR): ν = 3074 (m, arom. CH), 2935, 2869 (2 s, aliph. CH),
˜
(1R*,3R*,4R*,8S*,9S*,11S*,12S*,16R*)-6,14-Bis[2,6-bis(dec-9-
1640 (m, C=C), 1597 (s, arom.), 1450 (s, arom.), 1243 (s, C–O),
enyloxy)phenyl]-5,7,13,15-tetraoxa-6,14-diborahexacyclo[9.5.1.13,9
.
1095 (s, C–O), 776 (s, 3 arom. H) cm–1 1H NMR (500 MHz,
.
02,10.04,8.012,16]octadecane (19e): General procedure F, boronic acid
1e (139 mg, 323 μmol) and anti-tetraol 11 (36.6 mg, 162 μmol) in
dry methanol (9 mL) and dry toluene (4.5 mL). Raw yield: 167 mg.
CDCl3, 25 °C): δ = 1.28 (mc, 2 H, 17b-H, 18b-H), 1.51–1.63 [m, 8
H, O(CH2)2CH2], 1.69–1.85 (m, 8 H, OCH2CH2), 1.72 (br. s, 2 H,
2-H, 10-H), 1.93 (d, 2J = 12.7 Hz, 1 H, 17a-H), 2.11 (mc, 8 H,
IR (ATR): ν = 3076 (m, arom. CH), 2924, 2853 (2 s, aliph. CH),
˜
2
CH2CH=), 2.23 (d, J = 10.6 Hz, 1 H, 18a-H), 2.40 (s, 2 H, 1-H,
1640 (m, C=C), 1597 (s, arom.), 1451 (s, arom.), 1243 (s, C–O),
11-H), 2.51 (br. s, 2 H, 3-H, 9-H), 3.95 (t, J = 6.1 Hz, 4 H, OCH2Ј),
3.95 (t, J = 6.1 Hz, 4 H, OCH2ЈЈ), 4.29 (br. s, 2 H, 12-H, 16-H),
4.84 (br. s, 2 H, 4-H, 8-H), 4.94–5.00 (m, 4 H, CHHcis), 5.00–5.08
(m, 4 H, CHHtrans), 5.77–5.88 (m, 4 H, CH=), 6.45 (d, J = 8.3 Hz,
2 H, 3Ј,5Ј-H), 6.45 (d, J = 8.3 Hz, 2 H, 3ЈЈ,5ЈЈ-H), 7.21 (t, J =
8.3 Hz, 1 H, 4Ј-H), 7.21 (t, J = 8.3 Hz, 1 H, 4ЈЈ-H) ppm. 13C NMR
(125 MHz, CDCl3, 25 °C): δ = 25.46, 25.51 [2 t, O(CH2)2CЈH2,
O(CH2)2CЈЈH2], 27.77 (t, 17-C), 28.92, 28.97 (2 t, OCH2CЈH2,
OCH2CЈЈH2), 33.67, 33.69 (2 t, CЈH2CH=, CЈЈH2CH=), 34.82 (t,
18-C), 41.53 (d, 1-C, 11-C), 42.44 (d, 2-C, 10-C), 46.00 (d, 3-C, 9-
C), 68.26 (t, OCH2), 81.25 (d, 4-C, 8-C), 85.03 (d, 12-C, 16-C),
104.41, 104.44 (2 d, 3Ј,5Ј-C, 3ЈЈ,5ЈЈ-C), 114.79, 114.85 (2 t, CЈH2=,
CЈЈH2=), 131.70, 131.76 (2 d, 4Ј-C, 4ЈЈ-C), 138.85, 138.87 (2 d,
CЈH=, CЈЈH=), 163.18, 163.19 (2 s, 2Ј,6Ј-C, 2ЈЈ,6ЈЈ-C) ppm. Be-
cause of relaxation effects with the 11B isotope, the 1-C signal is
missing in the spectrum. MS (EI, 70 eV): m/z (%) = 790 (100)
[M]+, 708 (12) [M – C6H12]+, 628 (4) [M – C12H24]+, 544 (12) [M –
C18H36]+, 462 (43) [M – C24H48]+, 274 (12) [C18H26O2]+. MS (CI,
1094 (s, C–O), 775 (s, 3 arom. H) cm–1 1H NMR (500 MHz,
.
CDCl3, 25 °C): δ = 1.23–1.47 [m, 42 H, O(CH2)2(CH2)5, 17b-H,
2
18b-H], 1.69–1.78 (m, 10 H, OCH2CH2, 2-H, 10-H), 1.95 (d, J =
12.6 Hz, 1 H, 17a-H), 2.04 (mc, 8 H, CH2CH=), 2.25 (d, 2J =
10.9 Hz, 1 H, 18a-H), 2.41 (s, 2 H, 1-H, 11-H), 2.51 (br. s, 2 H, 3-
H, 9-H), 3.93 (t, J = 6.3 Hz, 8 H, OCH2), 4.29 (br. s, 2 H, 12-H,
16-H), 4.84 (br. s, 2 H, 4-H, 8-H), 4.89–4.96 (m, 4 H, CHHcis),
4.96–5.02 (mc, 4 H, CHHtrans), 5.81 (ddt, Jd = 16.9 Hz, Jd
=
10.2 Hz, Jt = 6.7 Hz, 4 H, CH=), 6.45 (d, J = 8.3 Hz, 4 H, 3Ј,5Ј-
H, 3ЈЈ,5ЈЈ-H), 7.21 (t, J = 8.3 Hz, 1 H, 4Ј-H), 7.21 (t, J = 8.3 Hz,
1 H, 4ЈЈ-H) ppm. 13C NMR (125 MHz, CDCl3, 25 °C): δ = 26.18,
26.18 [2 t, O(CH2)2CЈH2, O(CH2)2CЈЈH2], 27.73 (t, 17-C), 29.14,
29.17, 29.29, 29.30, 29.47, 29.48, 29.57, 29.59, 29.70, 29.77 [10 t,
OCH2CЈH2, O(CH2)3(CЈH2)4, OCH2CЈЈH2, O(CH2)3(CЈЈH2)4],
34.01 (t, CH2CH=), 34.85 (t, 18-C), 41.56 (d, 1-C, 11-C), 42.49 (d,
2-C, 10-C), 46.04 (d, 3-C, 9-C), 68.44, 68.51 (2 t, OCЈH2, OCЈЈH2),
81.23 (d, 4-C, 8-C), 85.04 (d, 12-C, 16-C), 104.43 (d, 3,5-C), 114.36,
114.40 (2 t, CЈH2=, CЈЈH2=), 131.67, 131.71 (2 d, 4Ј-C, 4ЈЈ-C),
139.34, 139.38 (2 d, CЈH=, CЈЈH=), 163.23, 163.26 (2 s, 2Ј,6Ј-C,
2ЈЈ,6ЈЈ-C) ppm. Because of relaxation effects with the 11B isotope,
the 1-C signal is missing in the spectrum. MS (EI, 70 eV): m/z (%)
= 1015 (100) [M]+. MS (CI, isobutane): m/z (%) = 1016 (9) [M +
H]+. MALDI-MS (Cl-CCA): m/z = 1054 [M + K]+, 1038 [M +
Na]+, 1016 [M + H]+. C64H96B2O8 (1014.71), calcd. C 75.73, H
9.53; found C 75.80, H 10.27.
isobutane): m/z (%) = 791 (2) [M + H]+, 275 (100) [C18H26O2
+
H]+. MS (ESI, CHCl3/MeOH): C48H64B2O8 (790.48), C48H64B2O8
+ Na+, calcd. 813.4680; found 813.4644 (Δ = –4.4 ppm).
C48H6410BBO8 + Na+, 812.4721; found 812.4698 (Δ = –2.8 ppm).
(1R*,3R*,4R*,8S*,9S*,11S*,12S*,16R*)-6,14-Bis[2,6-bis(oct-7-
enyloxy)phenyl]-5,7,13,15-tetraoxa-6,14-diborahexacyclo[9.5.1.13,9
.
02,10.04,8.012,16]octadecane (19d): General procedure F, boronic acid
1d (40.4 mg, 108 μmol) and anti-tetraol 11 (12.2 mg, 53.9 μmol) in
dry methanol (3 mL) and dry toluene (1.5 mL). Raw yield: 50.7 mg.
(1R*,3R*,4R*,8S*,9S*,11S*,12S*,16R*)-6,14-Bis[2,6-bis(undec-
10-enyloxy)phenyl]-5,7,13,15-tetraoxa-6,14-diborahexacyclo[9.5.1.
13,9.02,10.04,8.012,16]octadecane (19f): General procedure F, boronic
IR (ATR): ν = 3076 (m, arom. CH), 2926, 2855 (2 s, aliph. CH),
˜
1640 (m, C=C), 1597 (s, arom.), 1451 (s, arom.), 1242 (s, C–O), acid 1f (148 mg, 323 μmol) and anti-tetraol 11 (36.6 mg, 162 μmol)
1094 (s, C–O), 776 (s, 3 arom. H) cm–1 1H NMR (500 MHz,
in dry methanol (9 mL) and dry toluene (4.5 mL). Raw yield:
CDCl3, 25 °C): δ = 1.21–1.54 [m, 26 H, O(CH2)2(CH2)3, 17b-H, 172 mg. IR (ATR): ν = 3076 (m, arom. CH), 2923, 2853 (2 s, aliph.
.
˜
2
18b-H], 1.69–1.89 (m, 10 H, OCH2CH2, 2-H, 10-H), 1.94 (d, J =
CH), 1640 (m, C=C), 1597 (s, arom.), 1451 (s, arom.), 1242 (s, C–
12.6 Hz, 1 H, 17a-H), 2.06 (mc, 8 H, CH2CH=), 2.25 (d, 2J =
O), 1095 (s, C–O), 775 (s, 3 arom. H) cm–1. H NMR (500 MHz,
1
10.8 Hz, 1 H, 18a-H), 2.41 (s, 2 H, 1-H, 11-H), 2.51 (br. s, 2 H, 3- CDCl3, 25 °C): δ = 1.24–1.52 [m, 50 H, O(CH2)2(CH2)6, 17b-H,
2
H, 9-H), 3.93 (t, J = 6.3 Hz, 8 H, OCH2Ј), 4.29 (br. s, 2 H, 12-H,
18b-H], 1.69–1.78 (m, 10 H, OCH2CH2, 2-H, 10-H), 1.95 (d, J =
16-H), 4.84 (br. s, 2 H, 4-H, 8-H), 4.91–4.97 (mc, 4 H, CHHcis), 12.7 Hz, 1 H, 17a-H), 2.04 (mc, 8 H, CH2CH=), 2.25 (d, 2J =
4.97–5.05 (mc, 4 H, CHHtrans), 5.81 (mc, 4 H, CH=), 6.45 (d, J = 10.8 Hz, 1 H, 18a-H), 2.41 (s, 2 H, 1-H, 11-H), 2.51 (br. s, 2 H, 3-
8.3 Hz, 4 H, 3Ј,5Ј-H, 3ЈЈ,5ЈЈ-H), 7.21 (t, J = 8.3 Hz, 1 H, 4Ј-H),
H, 9-H), 3.93 (t, J = 6.4 Hz, 8 H, OCH2), 4.29 (br. s, 2 H, 12-H,
7.21 (t, J = 8.3 Hz, 1 H, 4ЈЈ-H) ppm. 13C NMR (125 MHz, CDCl3, 16-H), 4.84 (br. s, 2 H, 4-H, 8-H), 4.89–4.95 (m, 4 H, CHHcis),
25 °C): δ = 26.02, 26.03 [2 t, O(CH2)2CЈH2, O(CH2)2CЈЈH2] 29.06,
29.08, 29.10, 29.16, 29.39, 29.42 [6 t, OCH2CЈH2, O(CH2)3-
4.95–5.03 (m, 4 H, CHHtrans), 5.80 (mc, 4 H, CH=), 6.45 (d, J =
8.3 Hz, 4 H, 3Ј,5Ј-H), 7.21 (t, J = 8.3 Hz, 2 H, 4Ј-H) ppm. 13C
(CЈH2)2, OCH2CЈЈH2, O(CH2)3(CЈЈH2)2], 27.74 (t, 17-C), 33.91 (t, NMR (125 MHz, CDCl3, 25 °C): δ = 26.17, 26.19 [2 t, O(CH2)2-
CH2CH=), 34.87 (t, 18-C), 41.54 (d, 1-C, 11-C), 42.49 (d, 2-C, 10- CЈH2, O(CH2)2CЈЈH2], 27.74 (t, 17-C), 29.15, 29.16, 29.36, 29.40,
C), 46.05 (d, 3-C, 9-C), 68.38, 68.47 (2 t, OCЈH2, OCЈЈH2), 81.22 (d, 29.47, 29.49, 29.62, 29.63, 29.66, 29.67, 29.81, 29.87 [12 t,
4-C, 8-C), 85.06 (d, 12-C, 16-C), 104.42 (d, 3,5-C), 114.54, 114.57 (2 OCH2CЈH2, O(CH2)3(CЈH2)5, OCH2CЈЈH2, O(CH2)3(CЈЈH2)5],
t, CЈH2=, CЈЈH2=), 131.68, 131.73 (2 d, 4Ј-C, 4ЈЈ-C), 139.20 (d, 34.01 (t, CH2CH=), 34.85 (t, 18-C), 41.56 (d, 1-C, 11-C), 42.49 (d,
CH=), 163.23, 163.26 (2 s, 2Ј,6Ј-C, 2ЈЈ,6ЈЈ-C) ppm. Because of re-
laxation effects with the 11B isotope, the 1-C signal is missing in
the spectrum. MS (EI, 70 eV): m/z (%) = 903 (100) [M]+, 849 (20)
[M – C4H8]+, 793 (11) [M – C8H14]+, 683 (4) [M – C16H28]+, 572
(3) [M – C24H42]+, 462 (28) [M – C32H56]+, 330 (17) [C22H34O2]+.
MS (CI, isobutane): m/z (%) = 904 (Ͻ1) [M + H]+, 331 (100)
[C22H34O2 + H]+. MS (ESI, CHCl3/MeOH): C56H80B2O8 (902.60),
2-C, 10-C), 46.04 (d, 3-C, 9-C), 68.44, 68.50 (2 t, OCЈH2, OCЈЈH2),
81.22 (d, 4-C, 8-C), 85.04 (d, 12-C, 16-C), 104.42 (d, 3,5-C), 114.31,
114.35 (2 t, CЈH2=, CЈЈH2=), 131.66, 131.70 (2 d, 4Ј-C, 4ЈЈ-C),
139.38, 139.41 (2 d, CЈH=, CЈЈH=), 163.22, 163.26 (2 s, 2Ј,6Ј-C,
2ЈЈ,6ЈЈ-C) ppm. Because of relaxation effects with the 11B isotope,
the 1-C signal is missing in the spectrum. MS (EI, 70 eV): m/z (%)
= 1071 (100) [M]+. MS (CI, isobutane): m/z (%) = 1072 (15) [M +
Eur. J. Org. Chem. 2011, 5845–5859
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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