Efficient Synthesis of Anhydrorhodovibrin and Analogues

Abstract

The synthesis of anhydrorhodovibrin and two analogues has been achieved in a highly efficient manner using a new Horner–Wadsworth–Emmons reagent bearing the Weinreb amide.

Key words

polyene - carotenoid - Horner–Wadsworth–Emmons ­reaction - Weinreb amide

• References

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• 20 (R)-3: ¹H NMR (600 MHz, C₆D₆): δ = 6.60–6.79 (m, 5 H), 6.51 (d, J = 13.8 Hz, 1 H), 6.50 (d, J = 14.4 Hz, 1 H), 6.49 (d, J = 14.4 Hz, 1 H), 6.24–6.38 (m, 7 H), 5.91 (dt, J = 15.6, 7.2 Hz, 1 H), 5.75 (dt, J = 15.6, 7.2 Hz, 1 H), 5.24 (m, 1 H), 3.08 (s, 3 H), 2.32 (d, J = 7.2 Hz, 2 H), 2.20 (dt, J = 13.8, 7.2 Hz, 1 H), 1.97–2.15 (m, 3 H), 1.90 (s, 3 H), 1.89 (s, 3 H), 1.89 (s, 3 H), 1.88 (s, 6 H), 1.69 (s, 3 H), 1.60 (s, 3 H), 1.54–1.60 (m, 1 H), 1.44–1.51 (m, 1 H), 1.19–1.29 (m, 1 H), 1.10 (s, 6 H), 0.95 (d, J = 6.6 Hz, 3 H). ¹³C NMR (150 MHz, C₆D₆): δ = 138.5, 138.0, 137.9, 137.7, 136.9, 136.8, 136.7, 136.3, 135.7, 135.6, 133.6, 133.3, 133.1, 131.3, 131.0 (2 × C), 130.8, 130.6, 128.7, 128.3, 126.1, 125.6, 125.3, 125.2, 74.7, 49.1, 44.6, 41.1, 37.2, 33.4, 26.1, 25.8, 24.9, 19.7, 17.7, 13.1 (2 × C), 12.9 (2 × C), 12.8. HRMS (EI): m/z [M]⁺ calcd for [C₄₁H₆₀O]⁺: 568.4644; found: 568.4645; [α]_D ^25.1 +51.0 (c = 0.1, CHCl₃).
• 21 5: ¹H NMR (600 MHz, CDCl₃): δ = 6.55–6.66 (m, 4 H), 6.48 (dd, J = 15.0, 11.1 Hz, 1 H), 6.37 (d, J = 15.6 Hz, 1 H), 6.35 (d, J = 15.0 Hz, 1 H), 6.26 (d, J = 10.2 Hz, 1 H), 6.17–6.24 (3 H), 6.16 (d, J = 15.5 Hz, 1 H), 6.10 (d, J = 11.4 Hz, 1 H), 5.94 (d, J = 11.1 Hz, 1 H), 5.71 (dt, J = 15.5, 7.4 Hz, 1 H), 3.23 (s, 3 H), 2.32 (d, J = 7.4 Hz, 2 H), 1.98 (s, 3 H), 1.96 (s, 3 H), 1.94 (s, 3 H), 1.92 (s, 3 H), 1.82 (s, 3 H), 1.81 (s, 3 H), 1.15 (s, 6 H). ¹³C NMR (150 MHz, CDCl₃): δ = 137.9, 137.5 (2 × C), 136.6, 136.2, 136.1, 135.9, 135.2, 134.8, 133.0, 132.6, 131.4, 130.6, 130.3, 129.3, 126.0, 125.3, 125.1, 124.8, 124.6, 75.1, 49.3, 43.6, 26.3, 24.9, 18.6, 13.0, 12.9, 12.8 (2 × C). HRMS (FAB): m/z [M]⁺ calcd for [C₃₁H₄₄O]⁺: 432.3392; found: 432.3390.