Modified Iridoid Glycosides (Part-1): Syntheses of 4′-5′-unsaturated Iridoid Glycosides from Loganin and Arbortristoside-A

References

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• Spectral data of some selected compounds are given below: 7 MS (FAB) m/z 453 (M++1), 473 (M+Na); [α]D=-116.66 (C=0.10 in CHCl3); 1-H NMR (400 MHz, CDCl3), δ 9.30 (s, 1H, CHO), 7.43 (s, 1H, H-3), 6.06 (d, 3.4, 1H, H-4′), 5.63 (d, 4.4, 1H, H-1′), 5.48 (d, 3.9, 1H, H-1), 5.34 (t, 6.8, 1H, H-3′), 5.13 (t, 6.8, 1H, H-2′), 3.74 (s, 3H, OCH3), 3.18 (m, 1H, H-5), 2.58 (m, 2H, H-6), 2.22 (m, 1H, H-9), 2.75 (m, 1H, H-8), 2.10 (s, 6H, 2 × COCH 3), 1.15 (d, 7, 3H, H-10), 13C NMR (100 MHz, CDCl3), δ218.18 (C-7), 185.61 (CHO), 169.63 (OCOCH3),168.89, 166.30 (OCOCH3 × 2), 150.70 (C-3), 149.26 (C-5′), 115.74 (C-4′), 110.74 (C-4), 93.77 (C-1), 92.94 (C-1′), 68.16 (C-2′), 64.45 (C-3′), 51.29 (OCH3), 45.21 (C-9), 42.96 (C-8), 41.85 (C-6), 26.55 (C-5), 20.74, 20.37 (COCH3 × 2), 13.25 (C-10). 8b. MS (FAZm/z 457 (M++1), 479 (M++Na); [α]D=-106.68 (C=0.-11 in CHCl3), 1H NMR (400 MHz, CDCl3), δ7.45 (s, 1H, H-3), 5.58 (d, 2, 1H, H-1′), 5.28 (d, 5, 1H, H-1), 5.20 (d, 5, 1H, H-4′), 5.13 (bs, 1H, H-2′), 5.08 (bs, 1H, H-3′), 4.10 (q, 30, 12, 2H, H-6′), 3.88 (m, 1H, H-7), 3.71 (s, 3H, OCH3), 2.90 (m, 1H, H-5), 2.63 (m, 1H, H-6), 2.11 (s, 3H, OCOCH 3), 2.07 (s, 3H, OCOCH 3), 1.93 (m, 1H, H-8), 1.72 (m, 1H, H-9), 1.39 (m, 1H, H-6ß), 1.11 (d, 9, 3H, H-10), 13C NMR (100 MHz, CDCl3), δ 179.11 (COOCH3), 169.29 (OCOCH3), 167.55 (OCOCH3), 152.21 (C-5′), 151.84 (C-3), 111.21 (C-4), 96.85 (C-4′), 95.83 (C-1′), 91.76 (C-1), 79.46 (C-7), 68.39 (C-2′), 64.46 (C-3′), 62.24 (C-6′), 51.22 (OCH3), 46.13 (C-8), 43.19 (C-9), 42.08 (C-6), 32.18 (C-5), 20.91 (OCOCH3), 20.65 (OCOCH3), 18.42 (C-10). 12a MS (FAB); m/z; 415 (M++1), 437 (M++Na), [α] D=-60.81 (C=0.12 in CHCl3), 1H NMR (400 MHz, CDCl3), δ 7.38 (s, 1H, H-3), 5.48 (d, 3, 1H, H-1′), 5.20 (d, 5.9, 1H, H-1), 5.18 (te, 1H, H-7), 5.14 (d, 5, 1H, H-4′), 4.10 (bs, 2H, H-6′), 4.00 (bs, 1H, H-3′), 3.95 (bs, 1H, H-2′), 3.73 (s, 3H, OCH3), 3.09 (m, 1H, H-5), 2.38 (me, 1H, H-9), 2.32 (me, 1H, H-6), 2.07 (s, 3H, COCH3), 2.05 (m, 1H, H-8), 1.76 (m, 1H, H-6), 1.10 (d, 8, 3H, H-10); 13C NMR (100 MHz, CDCl3), δ 170.78 (COOMe), 167.27 (OCOCH3), 150.42 (C-3), 150.29 (C-5′), 111.42 (C-4), 100.20 (C-4′), 96.03 (C-10) 95.87 (C-1), 70.60 (C-7), 69.78 (C-2′), 65.88 (C-3′), 62.04 (C-6′), 51.35 (OCH3), 45.91 (C-9), 39.16 (C-8), 38.98 (C-6), 30.89 (C-5), 20.29 (OCOCH3), 13.07 (C-10). 12b MS(FAB); m/z; 395 (M++ Na), [α]D-9.75 (C=0.13 in CH3OH), 1H NMR (400 MHz, CD3OD), δ 7.39 (S, 1H, H-3), 5.26 (d, 6, 1H, H-1′), 5.23 (d, 5, 1H, H-1), 5.01 (d, 3, 1H, H-4′), 4.03 (m, 1H, H-7), 3.99 (t, 5, 1H, H-3′), 3.93 (s, 2H, H-6′), 3.69 (s, 3H, OCH3), 3.64 (t, 5, 1H, H-2′), 3.60 (m, 1H, H-5), 2.23 (m, 1H, H-6), 2.01 (m, 1H, H-9), 1.84 (m, 1H, H-8), 1.57 (m, 1H, H-6), 1.10 (d, 8, 3H, H-10); 13C NMR (100 MHz, CD3OD), δ 169.40 (COOCH3), 152.28 (C-5′), 151.84 (C-3), 140.27 (C-4), 101.00 (C-4′), 97.88 (C-1′ and C-1′), 74.98 (C-7), 72.01 (C-2′), 68.04 (C-3′), 62.31 (C-6′), 51.63 (OCH3), 46.50 (C-9), 42.83 (C-6), 42.29 (C-8), 32.21 (C-5), 13.38 (C-10). [e denotes overlapping with other signals]
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