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DOI: 10.1055/s-0028-1087669
Stereoselective Total Synthesis of (+)-Valienamine and (+)-4-epi-Valienamine via a Ring-Closing Enyne Metathesis Protocol
Publication History
Publication Date:
15 January 2009 (online)
Abstract
Stereoselective total synthesis of (+)-valienamine is reported utilizing Sharpless asymmetric dihydroxylation, diastereoselective Carreira alkynylation, and ring-closing enyne metathesis (RCEYM) as key steps from l-serine. A similar strategy is also reported for the first total synthesis of (+)-4-epi-valienamine.
Key words
Sharpless asymmetric dihydroxylation - Carreira alkynylation - Grubbs’ catalyst - ring-closing enyne metathesis - valienamine - 4-epi-valienamine
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References and Notes
Spectral data for selected compounds:
Compound 10b: light yellow syrup; [α]D
²5 +11.96
(c = 0.59, CHCl3). ¹H
NMR (300 MHz, CDCl3): δ = 6.01 (m,
2 H), 5.20-5.34 (m, 2 H), 4.89 (q, 1 H, J = 8.8,
15.4 Hz), 4.80 (dd, 1 H, J = 4.0,
7.0 Hz), 4.66-4.76 (m, 2 H), 4.50-4.62 (m, 2 H),
4.38 (br s, 1 H), 4.02 (t, 1 H, J = 3.3
Hz), 3.76-3.83 (m, 2 H), 3.46 (s, 3 H), 3.43 (s, 3 H),
3.36 (s, 3 H), 2.46 (d, 1 H, J = 1.8
Hz), 1.44 (s, 9 H). ¹³C NMR (75 MHz,
CDCl3): δ = 155.6, 135.1, 116.6, 99.3, 97.2,
94.4, 79.5, 79.4, 77.9, 76.0, 67.1, 56.8, 56.1, 55.9, 53.8, 28.3.
IR (neat): 3425, 3252, 2930, 2250, 2154, 1714, 1640, 1502, 1158,
1026 cm-¹. HRMS: m/z [M + Na]+ calcd
for C19H33NO8Na: 426.2103; found:
426.2107. Compound 11b: light yellow syrup;
[α]D
²5 -77.21
(c = 0.76, CHCl3). ¹H NMR
(300 MHz, CDCl3): δ = 6.24 (dd, 1 H, J = 11.0, 17.4 Hz), 5.78 (dd,
1 H, J = 3.0, 15.9 Hz), 5.44
(d, 1 H, J = 16.9 Hz), 5.10
(d, 1 H, J = 10.9 Hz), 4.90
(dd, 1 H, J = 3.4, 7.1 Hz),
4.60-4.82 (m, 6 H), 4.50 (br d, 1 H, J = 2.2
Hz), 4.29 (br s, 1 H), 4.10 (dd, 1 H, J = 2.2,
5.2 Hz), 3.86 (t, 1 H, J = 4.9
Hz), 3.42 (s, 3 H), 3.40 (s, 3 H), 3.39 (s, 3 H), 1.45 (s, 9 H). ¹³C
NMR (75 MHz, CDCl3): δ = 155.6, 136.6,
135.2, 129.5, 114.4, 96.4, 96.3, 95.9, 79.4, 73.5, 72.7, 72.4, 56.3, 55.8,
55.6, 29.0. IR (neat): 3416, 2925, 2854, 1717, 1609, 1510, 1156,
1024 cm-¹. HRMS: m/z [M + H]+ calcd
for C19H34NO8: 404.2284; found:
404.2279. Compound 13b: white solid; mp
94 ˚C; [α]D
²5 +22.7
(c = 0.62, CHCl3). ¹H NMR
(300 MHz, CDCl3): δ = 5.87 (d, 1 H, J = 4.4 Hz), 5.79 (br d, 1 H, J = 8.4 Hz), 5.43 (dd, 1 H, J = 6.4, 9.4 Hz), 5.34 (d, 1
H, J = 6.3 Hz), 4.98-5.10
(m, 2 H), 4.63 (d, 1 H, J = 13.2
Hz), 4.36 (d, 1 H, J = 13.2
Hz), 2.01-2.06 (m, 15 H). ¹³C
NMR (75 MHz, CDCl3): δ = 170.3, 170.2,
170.1, 169.9, 169.8, 134.3, 126.1, 71.2, 69.0, 68.5, 62.9, 44.8,
23.3, 20.7. IR (neat): 3287, 2925, 1746, 1658, 1371, 1225, 1031
cm-¹. HRMS: m/z [M + Na]+ calcd
for C17H23NO9Na: 408.1270; found:
408.1263. Compound 10a: syrupy liquid; [α]D
²5
-187.0
(c = 0.55, CHCl3). ¹H
NMR (300 MHz, CDCl3): δ = 5.79-5.97
(m, 1 H), 5.15-5.32 (m, 2 H), 4.91 (q, 1 H, J = 8.3, 15.1 Hz), 4.75 (dd,
3 H, J = 6.0, 17.3 Hz), 4.60
(t, 2 H, J = 6.8, 15.1 Hz),
4.37-4.46 (m, 1 H), 3.91 (t, 1 H, J = 5.2
Hz), 3.78 (m, 2 H), 3.44 (s, 3 H), 3.37 (m, 6 H), 2.44 (d, 1 H, J = 2.2 Hz), 1.44 (s, 9 H). ¹³C
NMR (75 MHz, CDCl3): δ = 155.3, 134.9,
112.3, 98.6, 96.9, 92.7, 79.8, 79.1, 78.4, 77.2, 66.8, 57.4, 56.7,
56.0, 52.9, 28.2. IR (neat): 3438, 3210, 2927, 2852, 2140, 1715,
1610, 1506, 1156, 1026 cm-¹. HRMS: m/z calcd for C19H34NO8:
404.2284; found: 404.2291. Compound 11a:
light yellow syrup; [α]D
²5 +62.68 (c = 2.6, CHCl3). ¹H
NMR (300 MHz, CDCl3): δ = 6.27 (dd, 1
H, J = 11.0, 17.5 Hz), 5.80
(br d, 1 H, J = 2.8 Hz), 5.44
(d, 1 H, J = 17.5 Hz), 5.06-5.12
(m, 2 H), 4.80 (d, 1 H, J = 7.0 Hz),
4.60-4.74 (m, 6 H), 4.28 (br s, 1 H), 4.10 (dd, 1 H, J = 2.1, 5.2 Hz), 3.86 (t, 1
H, J = 5.2 Hz), 3.42 (s, 3 H),
3.41 (s, 3 H), 3.39 (s, 3 H), 1.45 (s, 9 H). ¹³C
NMR (75 MHz, CDCl3): δ = 155.4, 136.8,
133.4, 129.0, 112.6, 97.5, 96.9, 96.3, 80.1, 74.7, 71.9, 71.0, 57.2,
56.0, 55.7, 28.3. IR (neat): 3366, 2925, 1714, 1158, 1020 cm-¹.
HRMS: m/z [M + H]+ calcd
for C19H34NO8: 404.2284; found:
404.2280. Compound 13a: thick white syrup; [α]D
²5 +69.6
(c = 0.58, CHCl3). ¹H
NMR (300 MHz, CDCl3): δ = 5.99 (d,
1 H, J = 5.3 Hz), 5.82 (d, 1
H, J = 8.3 Hz), 5.44 (dd, 1
H, J = 6.8, 11.5 Hz), 5.27 (br
dd, 1 H, J = 4.1, 6.2 Hz), 4.96-5.07
(m, 2 H), 4.66 (dd, 1 H, J = 1.5,
12.8 Hz), 4.33 (dd, 1 H, J = 1.5,
13.6 Hz), 2.07 (s, 3 H), 2.06 (s, 3 H), 2.05 (s, 3 H), 2.02 (s,
3 H), 2.00 (s, 3 H). ¹³C NMR (75 MHz,
CDCl3): δ = 170.5, 170.2, 170.1, 169.9,
169.8, 132.2, 127.0, 72.7, 70.9, 66.0, 62.2, 46.7, 23.1, 20.6. IR
(neat): 3447, 2963, 1742, 1647, 1260, 1020 cm-¹.
HRMS: m/z [M + Na]+ calcd
for C17H23NO9Na: 408.1270; found:
408.1265.