The Journal of Organic Chemistry
Page 28 of 67
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the procedure detailed for the preparation of compound 24 from alcohol 23, alcohol 28 (92
mg, 0.2 mmol) was treated with iPr NEt (77 μL, 0.44 mmol) and MOM-Cl (12 μL, 0.15
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mmol) to afford MOM ether 29 (93 mg, 0.18 mmol) in 93% yield as a colourless liquid.
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TLC: R 0.2 (5% EtOAc/Hexane); [α]
-9.8 (c 0.5, CHCl ); IR (Neat) 2897, 1622, 2114,
3
f
D
−
1 1
1
512, 1247, 1030, 822 cm ; H NMR (400 MHz, CDCl ) δ 7.26 (d, J = 8.7 Hz, 2H), 6.88 (d,
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J = 8.7 Hz, 2H), 5.73 (dd, J = 15.5, 6.6 Hz, 1H), 5.59 (dd, J = 15.5, 7.6 Hz, 1H), 5.54 – 5.35
m, 2H), 5.00 – 4.93 (m, 1H), 4.85 – 4.80 (m, 1H), 4.68 (d, J = 6.9 Hz, 2H), 4.64 (d, J = 6.7
Hz, 1H), 4.51 (d, J = 6.7 Hz, 1H), 4.42 (s, 2H), 4.34 – 4.25 (m, 2H), 4.24 – 4.18 (m, 1H),
.80 (s, 3H), 3.63 – 3.54 (m, 2H), 3.54 – 3.48 (m, 1H), 3.37 (s, 3H), 3.34 (s, 3H), 2.65 (dd, J
= 15.4, 5.7 Hz, 1H), 2.35 – 2.25 (m, 1H), 2.22 (t, J = 5.7 Hz, 2H), 1.94 – 1.78 (m, 3H), 1.75 –
(
3
13
1
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.68 (m, 1H), 1.65 (dd, J = 5.9, 0.9 Hz, 3H), 1.60 – 1.47 (m, 2H); C{ H} NMR (125 MHz,
CDCl ) δ 159.1, 151.3, 133.3, 131.8, 130.5, 129.3, 127.6, 126.9, 113.7, 104.4, 95.3, 93.8,
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81.0, 78.1, 77.1, 73.2, 72.6, 66.3, 55.5, 55.4, 55.2, 40.1, 37.6, 35.7, 31.2, 29.8, 18.0; MS
+
+
(
ESI-TOF) m/z: 527 [M+Na] . HRMS (ESI-TOF) m/z: [M+Na] calcd for C H O Na:
29 44 7
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27.2985; found: 527.2998.
S,E)-3-(Methoxymethoxy)-5-((2R,5R)-5-((S,E)-3-(methoxymethoxy)hept-5-en-1-yl)-4-
(
methylenetetrahydrofuran-2-yl)pent-4-en-1-ol 30: Following the procedure detailed for
the preparation of compound 25 from PMB ether 24, compound 29 (70 mg, 0.14 mmol) was
treated with DDQ (48 mg, 0.21 mmol) to afford alcohol 30 (43 mg, 0.11 mmol) in 80% yield
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as a colourless liquid. TLC: R 0.2 (20% EtOAc/Hexane); [α]
-27.1 (c 0.3, CHCl ); IR
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f
D
−1
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(
Neat) 3281, 2897, 1615, 1512, 1247, 1030, 822 cm ; H NMR (500 MHz, CDCl ) δ 5.75
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(dd, J = 15.5, 6.6 Hz, 1H), 5.63 (dd, J = 15.5, 7.2 Hz, 1H), 5.54 – 5.37 (m, 2H), 4.99 – 4.95
(m, 1H), 4.89 – 4.78 (m, 1H), 4.69 (d, J = 6.7 Hz, 1H), 4.67 (d, J = 6.9 Hz, 1H), 4.64 (d, J =
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1
.9 Hz, 1H), 4.53 (d, J = 6.7 Hz, 1H), 4.33 – 4.25 (m, 3H), 3.83 – 3.77 (m, 1H), 3.74 (dt, J =
1.1, 5.5 Hz, 1H), 3.58 (dt, J = 11.5, 5.7 Hz, 1H), 3.39 (s, 3H), 3.37 (s, 3H), 2.68 (dd, J =
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