Synthesis of Vinyllactones
via Allylic Oxidation of Alkenoic Acids

Martina Bischop; Jörg Pietruszka

doi:10.1055/s-0031-1289549

LETTER

Synthesis of Vinyllactones via Allylic Oxidation of Alkenoic Acids

Martina Bischop, Jörg Pietruszka*
Institut für Bioorganische Chemie der Heinrich-Heine-Universität Düsseldorf im Forschungszentrum Jülich, Stetternicher Forst, Geb. 15.8, 52426 Jülich, Germany
Fax: +49(2461)616196; e-Mail: j.pietruszka@fz-juelich.de;

Abstract

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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

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References

References and Notes

Selected examples:

1a Corey EJ. Guzman-Perez A. Lazerwith SE. J. Am. Chem. Soc. 1997, 119: 11769

1b Jacobo SH. Chang C.-T. Lee G.-J. Lawson JA. Powell WS. Pratico D. FitzGerald GA. Rokach J.
J. Org. Chem. 2006, 71: 1370

1c Mac DH. Samineni R. Petrignet J. Srihari P. Chandrasekhar S. Yadav JS. Grée R. Chem Commun. 2009, 4717

1d Fischer T. Pietruszka J. Adv. Synth. Catal. 2007, 348: 4388

1e Larock RC. Hightower TR. J. Org. Chem. 1993, 58: 5298

1f Annby U. Stenkula M. Andersson C.-M. Tetrahedron Lett. 1993, 34: 8545

1g For a recent review on Pd-catalyzed allylic C-H bond activation, see: Liu G. Wu Y. Top. Curr. Chem. 2010, 292: 195

Leading references:

2a Stang EM. White MC. Angew. Chem. Int. Ed. 2011, 50: 547

2b Stang EM. White MC. Nat. Chem. 2009, 1: 2094

2c Fraunhoffer KJ. Prabagaran N. Sirois LE. White MC. J. Am. Chem. Soc. 2006, 128: 9032

3a Korpak M. Pietruszka J. Adv. Synth. Catal. 2011, 353: 1420

3b Bischop M. Doum V. Nordschild née Rieche ACM. Pietruszka J. Sandkuhl D. Synthesis 2010, 527

3c Pietruszka J. Rieche ACM. Adv. Synth. Catal. 2008, 350: 1407

3d Pietruszka J. Rieche ACM. Schöne N. Synlett 2007, 2525

3e Pietruszka J. Wilhelm T. Synlett 2003, 1698

4 Walborsky HM. Topolski M. Hamdouchi C. Pankowski J. J. Org. Chem. 1992, 57: 6188

5a For compound 9a, see: DeMartino MP. Chen K. Baran PS. J. Am. Chem. Soc. 2008, 130: 11546

5b For compounds 9b-e, see: Kaga H. Miura M. Orito K. J. Org. Chem. 1989, 54: 3477

6 For a recent review, see: Caddick S. Fitzmaurice R. Tetrahedron 2009, 65: 3325

7 Covell Dustin J. White MC. Angew. Chem. Int. Ed. 2008, 47: 6448

8 Hiebel M.-A. Pelotier B. Goekjian P. Piva O. Eur. J. Org. Chem. 2008, 713

9 Wang Y.-G. Kobayashi Y. Org. Lett. 2002, 4: 4615

10 The syn isomer was recently utilized for the synthesis of the lyngbouillodide macrolactone core: Webb D. van den Heuvel A. Koegl M. Ley SV. Synlett 2009, 2320

11 Guerlavais V. Carroll PJ. Joullié MM. Tetrahedron: Asymmetry 2002, 13: 675

12a Fürstner A. Radkowski K. Wirtz C. Goddard R. Lehmann CW. Mynott R. J. Am. Chem. Soc. 2002, 124: 7061

12b Evans DA. Weber AE. J. Am. Chem. Soc. 1987, 109: 7151

12c Macritchie JA. Silcock A. Willis CL. Tetrahedron: Asymmetry 1997, 8: 3895

13 Nagai K. Doi T. Sekiguchi T. Namatame I. Sunazuka T. Tomoda H. Omura S. Takahashi T. J. Comb. Chem. 2005, 8: 103

14a Garber SB. Kingsbury JS. Gray BL. Hovedya AH. J. Am. Chem. Soc. 2000, 122: 8168

14b Gessler S. Randl S. Blechert S. Tetrahedron Lett. 2000, 41: 9973

15 Matsuo J.-i. Aizawa Y. Tetrahedron Lett. 2005, 46: 407

16a Hlubucek JR. Robertson AV. Aust. J. Chem. 1967, 20: 2199

16b Bose DS. Reddy AVN. Srikanth B. Synthesis 2008, 2323

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]⁺.

18 For a recent SAR study, see: de Fatima A. Modolo LV. Conegero LS. Pilli RA. Ferreira CV. Kohn LK. de Carvalho JE. Curr. Med. Chem. 2006, 13: 3371

19 The synthesis of isomers of compound 25 was recently reported: Diba AK. Noll C. Richter M. Gieseler MT. Kalesse M. Angew. Chem. 2010, 122: 8545