Synthesis of Vinyllactones via Allylic Oxidation of Alkenoic Acids

Abstract

A one-step access to vinyllactones is described utilizing the Pd-catalyzed allylic oxidation of alkenoic acids. The influence of ring size as well as the olefin configuration is investigated culminating in the synthesis of goniothalamin analogues.

Key words

allyl complexes - catalysis - lactones - oxidation - palladium

References and Notes

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17

Selected Data for Acid 23
[α]_D ^²0 +17.2 (c 0.96, CHCl₃). IR (film): ν_max = 3073, 2977, 2935, 2861, 2648, 1702, 1642, 1465, 1417, 1381, 1290, 1236, 1191, 996, 910, 812, 742 cm^-¹. ^¹H NMR (600 MHz, CDCl₃): δ = 1.19 (d, ^³ J _Me,2 = 7.0 Hz, 3 H, CH₃), 1.41-1.49 (m, 3 H, 3-H_a, 4-H), 1.66-1.73 (m, 1 H, 3-H_b), 2.05-2.09 (m, 2 H, 5-H), 2.47 (m_c, 1 H, 2-H), 4.96 (ddt, ^³ J _7E,6 = 10.2 Hz, ^² J _{7 E ,7 Z}  = 2.0 Hz, ⁴ J _{7 E ,5} = 1.2 Hz, 1 H, 7-H _E ), 5.01 (ddd, ^³ J _{7 Z ,6} = 17.1 Hz, ^² J _{7 Z ,7 E}  = 2.0 Hz, ⁴ J _{7 Z ,5} = 1.6 Hz, 1 H, 7-H _Z ), 5.80 (ddt, ^³ J _{6,7 Z}  = 17.1 Hz, ^³ J _{6,7 E}  = 10.2 Hz, ^³ J _6,5 = 6.7 Hz, 1 H, 6-H), 11.5 (br s, 1 H, COOH) ppm. ^¹³C NMR (151 MHz, CDCl₃): δ = 16.9 (CH₃), 26.4 (C-4), 32.9 (C-3), 33.6 (C-5), 39.2 (C-2), 114.8 (C-7), 138.4 (C-6), 183.0 (C-1) ppm.
MS (EI, 70 eV): m/z (%) = 124 (2) [M - OH]⁺, 101 (3) [C₅H₈O₂]⁺, 96 (6) [C₇H₁₃]⁺, 87 (13) [C₄H₆O₂]⁺, 74 (100) [C₃H₅O₂]⁺, 69 (90) [C₄H₆O]⁺, 55 (38) [C₃H₄O]⁺. Anal. Calcd for C₈H₁₄O₂ (142.20): C, 67.57; H, 9.92. Found: C, 67.52; H, 10.02.
Selected Data for Vinyllactone 25 ^¹9
IR (film): ν_max = 3027, 2967, 2935, 2875, 1729, 1599, 1578, 1495, 1450, 1376, 1363, 1239, 1184, 1100, 1073, 1011, 969, 933, 749, 694 cm^-¹. MS (EI, 70 eV): m/z (%) = 216 (73) [M]⁺, 187 (5) [C₁₃H₁₆O]⁺, 160 (7) [C₁₁H₁₂O]⁺, 146 (37) [C₁₀H₁₀O]⁺, 129 (77) [C₁₀H₁₀]⁺, 115 (54) [C₉H₈]⁺, 104 (100) [C₈H₇]⁺, 91 (61) [C₇H₆]⁺, 77 (30) [C₆H₅]⁺, 56 (80) [C₄H₈]⁺. Anal. Calcd for C₁₄H₁₆O₂ (216.28): C, 77.75; H, 7.46. Found: C, 77.52; H, 7.35.
Isomer 25a
[α]_D ^²0 +18.2 (c 0.60, CHCl₃). ^¹H NMR (600 MHz, CDCl₃): δ = 1.35 (d, ^³ J _Me,3 = 7.1 Hz, 3 H, CH₃), 1.63-1.70 (m, 1 H, 4-H_a), 1.78-1.85 (m, 1 H, 5-H_a), 2.08-2.12 (m, 2 H, 4-H_b, 5-H_b), 2.53 (ddq, ^³ J _3,4a = 8.8 Hz, ^³ J _3,4b = 7.0 Hz, ^³ J _3,Me = 7.0 Hz, 1 H, 3-H), 4.97 (dddd, ^³ J _6,5a = 10.9 Hz, ^³ J _{6,1 ′} = 6.2 Hz, ^³ J _6,5b = 3.4 Hz, ⁴ J _{6,2 ′} = 1.4 Hz, 1 H, 6-H), 6.21 (dd, ^³ J _{1 ′ ,2 ′} = 16.0 Hz, ^³ J _{1 ′ ,6} = 6.2 Hz, 1 H, 1′-H), 6.66 (dd, ^³ J _{2 ′ ,1 ′} = 16.0 Hz, ⁴ J _{2 ′ ,6} = 1.4 Hz, 1 H, 2′-H), 7.25-7.28 (m, 1 H, arom. 4-CH), 7.31-7.34 (m, 2 H, arom. CH), 7.37-7.39 (m, 2 H, arom. CH) ppm. ^¹³C NMR (151 MHz, CDCl₃): δ = 14.3 (CH₃), 28.2 (C-4), 29.5 (C-5), 36.0 (C-3), 81.5 (C-6), 126.6 (arom. CH), 127.5 (C-1′), 128.1 (arom. 4-CH), 128.7 (arom. CH), 131.9 (C-2′), 136.0 (arom. C_ipso), 174.0 (C-2) ppm.
Isomer 25b
[α]_D ^²0 +29.2 (c 1.35, CHCl₃). ^¹H NMR (600 MHz, CDCl₃): δ = 1.27 (d, ^³ J _Me,3 = 6.8 Hz, 3 H, CH₃), 1.58-1.64 (m, 1 H, 4-H_a), 1.82-1.89 (m, 1 H, 5-H_a), 2.05-2.16 (m, 2 H, 4-H_b, 5-H_b), 2.66 (ddq, ^³ J _3,4a = 10.5 Hz, ^³ J _3,4b = 7.8 Hz, ^³ J _3,Me = 6.8 Hz, 1 H, 3-H), 5.00 (dddd, ^³ J _6,5a = 9.9 Hz, ^³ J _{6,1 ′} = 6.0 Hz, ^³ J _6,5b = 4.0 Hz, ⁴ J _{6,2 ′} = 1.4 Hz, 1 H, 6-H), 6.20 (dd, ^³ J _{1 ′ ,2 ′} = 16.0 Hz, ^³ J _{1 ′ ,6} = 6.0 Hz, 1 H, 1′-H), 6.67 (dd, ^³ J _{2 ′ ,1 ′} = 16.0 Hz, ⁴ J _{2 ′ ,6} = 1.4 Hz, 1 H, 2′-H), 7.25-7.28 (m, 1 H, arom. 4-CH), 7.31-7.34 (m, 2 H, arom. CH), 7.37-7.39 (m, 2 H, arom. CH) ppm. ^¹³C NMR (151 MHz, CDCl₃): δ = 16.4 (CH₃), 25.4 (C-4), 27.5 (C-5), 33.7 (C-3), 78.3
(C-6), 126.4 (arom. CH), 126.6 (C-1′), 128.1 (arom. 4-CH), 128.7 (arom. CH), 132.1 (C-2′), 136.0 (arom. C_ipso), 175.4 (C-2) ppm.
Selected Data for Goniothalamin Analogue 26
[α]_D ^²0 -152.5 (c 1.5, CHCl₃). IR (film): ν_max = 3028, 2926, 1710, 1599, 1578, 1495, 1450, 1362, 1338, 1230, 1144, 1109, 1081, 1042, 1014, 968, 918, 861, 753, 731, 693 cm^-¹. ^¹H NMR (600 MHz, CDCl₃): δ = 1.95 (dt, ⁴ J _Me,4 = 2.2 Hz, ⁵ J _Me,5 = 1.5 Hz, 3 H, CH₃), 2.48-2.52 (m, 2 H, 5-H), 5.05 (m_c, 1 H, 6-H), 6.27 (dd, ^³ J _{1 ′ ,2 ′} = 15.9 Hz, ^³ J _{1 ′ ,6} = 6.3 Hz, 1 H, 1′-H), 6.61 (m_c, 1 H, 4-H), 6.71 (dd, ^³ J _{2 ′ ,1 ′} = 15.9 Hz, ⁴ J _{2 ′ ,6} = 1.4 Hz, 1 H, 2′-H), 7.26-7.29 (m, 1 H, arom. 4-CH), 7.32-7.34 (m, 2 H, arom. CH), 7.38-7.40 (m, 2 H, arom. CH) ppm. ^¹³C NMR (151 MHz, CDCl₃): δ = 17.1 (CH₃), 30.3 (C-5), 78.0 (C-6), 126.0 (C-1′), 126.9, 128.3, 128.8 (arom. CH), 128.9 (C-3), 132.8 (C-2′), 135.9 (arom. C_ipso), 138.5 (C-4), 165.5 (C-2) ppm. MS (EI, 70 eV): m/z (%) = 214 (36) [M]⁺, 186 (10) [C₁₂H₁₁O₂]⁺, 171 (4) [C₁₃H₁₄]⁺, 129 (12) [C₁₀H₁₀]⁺, 115 (11) [C₉H₈]⁺, 104 (21) [C₈H₇]⁺, 89 (29) [C₇H₆]⁺, 82 (100) [C₅H₆O]⁺, 54 (24) [C₄H₆]⁺.