Stereochemical assignment of topsentolide C2 by stereodivergent synthesis of its four diastereomers

Tetrahedron Letters

Volumn 54, Issue 50, 2013, Pages 6878-6881

  Towada, Ryo ^a   Kurashina, Yusuke ^a   Kuwahara, Shigefumi ^a  

^a TOHOKU UNIVERSITY   (Japan)

Author keywords

Cytotoxic; Lactonization; Oxylipin; Topsentolide; Total synthesis

Indexed keywords

ACID; COMMON CHIRAL SECO ACID; CYTOTOXIC AGENT; LACTONE DERIVATIVE; TOPSENTIA EXTRACT; TOPSENTOLIDE C2; UNCLASSIFIED DRUG;

ARTICLE; DIASTEREOISOMER; DRUG CYTOTOXICITY; DRUG SYNTHESIS; HUMAN; LACTONIZATION; MARINE SPECIES; NONHUMAN; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; PHYSICAL CHEMISTRY; SPONGE (PORIFERA); STEREOCHEMISTRY; TOPSENTIA;

EID: 84900311443     PISSN: 00404039     EISSN: 18733581     Source Type: Journal    
DOI: 10.1016/j.tetlet.2013.10.032     Document Type: Article

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14. Physical and spectral data. 1: [α]28D –95.8 (c 0.570, MeOH); 1H NMR (400 MHz, CD3OD) δ 0.90 (3H, t, J = 6.9 Hz), 1.25–1.40 (6H, m), 1.70–1.82 (1H, m), 2.00–2.24 (7H, m), 2.30–2.58 (4H, m), 3.29 (3H, s), 3.47–3.55 (2H, m), 5.25–5.31 (1H, m), 5.42–5.53 (4H, m), 5.69 (1H, ddd, J = 15.6, 7.7, 1.2 Hz), 5.87 (1H, dd, J = 15.6, 5.7 Hz); 13C NMR (100 MHz, CD3OD) δ 14.4, 23.6, 26.3, 27.6, 28.4, 30.4, 31.8, 32.7, 34.4, 35.6, 57.0, 74.0, 74.8, 85.7, 125.6, 126.6, 130.3, 132.7, 134.0, 136.2, 175.6; HRMS (FAB) m/z calcd for C21H34O4Na ([M+Na]+) 373.2355, found 373.2351. 12-epi-1: [α]27D –55 (c 0.47, MeOH); 1H NMR (400 MHz, CD3OD) δ 0.90 (3H, t, J = 6.9 Hz), 1.25–1.40 (6H, m), 1.70–1.82 (1H, m), 2.01–2.24 (7H, m), 2.25–2.41 (2H, m), 2.42–2.58 (2H, m), 3.28 (3H, s), 3.54 (1H, dd, J = 7.6, 4.3 Hz), 3.63 (1H, dt, J = 7.6, 4.8 Hz), 5.26–5.32 (1H, m), 5.40–5.53 (4H, m), 5.74 (1H, dd, J = 15.7, 7.6 Hz), 5.85 (1H, dd, J = 15.7, 5.4 Hz); 13C NMR (100 MHz, CD3OD) δ 14.4, 23.6, 26.3, 27.6, 28.5, 30.5, 31.8, 32.7, 34.4, 35.6, 56.9, 74.0, 74.5, 85.8, 125.6, 126.6, 129.7, 132.8, 134.4, 136.2, 175.7; HRMS (FAB) m/z calcd for C21H34O4Na ([M+Na]+) 373.2355, found 373.2359. 8-epi-1: [α]29D +86.8 (c 1.33, MeOH); 1H NMR (400 MHz, CD3OD) δ 0.90 (3H, t, J = 6.9 Hz), 1.25–1.40 (6H, m), 1.70–1.82 (1H, m), 2.00–2.24 (7H, m), 2.30–2.58 (4H, m), 3.29 (3H, s), 3.47–3.55 (2H, m), 5.24–5.30 (1H, m), 5.42–5.53 (4H, m), 5.70 (1H, ddd, J = 15.8, 7.4, 1.0 Hz), 5.87 (1H, dd, J = 15.8, 5.5 Hz); 13C NMR (100 MHz, CD3OD) δ 14.4, 23.6, 26.3, 27.6, 28.4, 30.4, 31.8, 32.7, 34.4, 35.5, 57.0, 73.9, 74.9, 85.7, 125.6, 126.6, 130.1, 132.7, 134.0, 136.2, 175.7; HRMS (FAB) m/z calcd for C21H34O4Na ([M+Na]+) 373.2355, found 373.2354. 8,12-bis-epi-1: [α]28D +66.2 (c 0.520, MeOH); 1H NMR (400 MHz, CD3OD) δ 0.90 (3H, t, J = 6.8 Hz), 1.25–1.40 (6H, m), 1.70–1.82 (1H, m), 2.01–2.24 (7H, m), 2.25–2.41 (2H, m), 2.42–2.58 (2H, m), 3.29 (3H, s), 3.54 (1H, dd, J = 7.6, 4.5 Hz), 3.62 (1H, dt, J = 7.6, 4.8 Hz), 5.25–5.31 (1H, m), 5.40–5.53 (4H, m), 5.73 (1H, dd, J = 15.8, 7.7 Hz), 5.85 (1H, dd, J = 15.8, 5.6 Hz); 13C NMR (100 MHz, CD3OD) δ 14.4, 23.6, 26.3, 27.6, 28.5, 30.4, 31.8, 32.7, 34.4, 35.6, 56.9, 74.0, 74.5, 85.9, 125.6, 126.6, 129.7, 132.8, 134.4, 136.2, 175.7; HRMS (FAB) m/z calcd for C21H34O4Na ([M+Na]+) 373.2355, found 373.2353.
15. 2 by MeOH at the allylic C11 position with inversion of configuration.
16. Unfortunately, the specific rotation values of 8-epi-1 [α]29D +86.8 (c = 1.33, MeOH) and 1 {[α]28D = –95.8 (c = 0.570, MeOH) were both far different from that reported for topsentolide C2 {[α]23D = +14.5 (c = 0.27, MeOH)}. Remeasurement of the specific rotation of authentic topsentolide C2 is needed to solve the discrepancy.