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Synlett 2009(2): 209-212  
DOI: 10.1055/s-0028-1087669
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Stereoselective Total Synthesis of (+)-Valienamine and (+)-4-epi-Valienamine via a Ring-Closing Enyne Metathesis Protocol

Palakodety Radha Krishna*, P. Srinivas Reddy
D-206/B, Discovery Laboratory, Organic Chemistry Division III, Indian Institute of Chemical Technology, Hyderabad 500607, India
Fax: +91(40)27160387; e-Mail: prkgenius@iict.res.in;
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Publication History

Received 15 September 2008
Publication Date:
15 January 2009 (online)

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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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18

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.