Asymmetric Synthesis of the Diene Unit of Methyl Sartortuoate via a Temperature-Sensitive Intramolecular Horner-Wadsworth-Emmons (HWE) Reaction

Hequan Yao; Yuan Gao; Peng Liu; Bingfeng Sun; Xingxiang Xu

doi:10.1055/s-2007-967970

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Synlett 2007(4): 0571-0574
DOI: 10.1055/s-2007-967970

LETTER

Asymmetric Synthesis of the Diene Unit of Methyl Sartortuoate via a Temperature-Sensitive Intramolecular Horner-Wadsworth-Emmons (HWE) Reaction

Hequan Yao, Yuan Gao, Peng Liu, Bingfeng Sun, Xingxiang Xu*
Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, P. R. of China
Fax: +86(21)64166128; e-Mail: xuxx@mail.sioc.ac.cn;

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Publication History

Received 15 November 2006
Publication Date:
21 February 2007 (online)

Abstract
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Abstract

The asymmetric synthesis of the diene unit of methyl sartortuoate is described. A temperature-sensitive intramolecular Horner-Wadsworth-Emmons reaction was employed for the construction of the 14-membered ring. A Payne rearrangement of an 2,3-epoxy alcohol was utilized for the installation of the hydroxyl group at the C14 position of the diene unit.

Key words

asymmetric synthesis - methyl sartortuoate - diene unit - HWE reaction - Payne rearrangement

References and Notes

1a Su J. Long K. Peng T. Zheng Q. Lin X. Acta Chim. Sin. 1985, 43: 796

Crossref Search in Google Scholar
1b Su J. Long K. Peng T. Zeng L. Zheng Q. Lin X. Sci. Sin., Ser. B (Engl. Ed.) 1988, 31: 1172

Crossref Search in Google Scholar
1c Su J. Long K. Peng T. He CH. Clardy J. J. Am. Chem. Soc. 1986, 108: 177

Crossref Search in Google Scholar
For other related compounds, see:
2a Kusumi T. Igari M. Ishitsuka MO. Itezono Y. Nakayama N. Kakisawa H. J. Org. Chem. 1990, 55: 6286

Crossref Search in Google Scholar
2b Leone PA. Bowden BF. Carrol AR. Coll JC. Meehan GV. J. Nat. Prod. 1993, 56: 521

Crossref Search in Google Scholar
2c Zeng L. Lan W. Su J. Zhang G. Feng X. Liang Y. Yang X. J. Nat. Prod. 2004, 67: 1915

Crossref Search in Google Scholar
2d Feller M. Rudi A. Berer N. Goldberg I. Stein Z. Benayahu Y. Schleyer M. Kashman Y. J. Nat. Prod. 2004, 67: 1303

Crossref Search in Google Scholar
2e Ishitsuka MO. Kusumi T. Kakisawa H. Tetrahedron Lett. 1991, 32: 2917

Crossref Search in Google Scholar
For synthetic studies on biscembranoids by the Nakata’s group, see:
3a Yasuda M. Ide M. Matsumoto Y. Nakata M. Synlett 1997, 899

Crossref
3b Yasuda M. Ide M. Matsumoto Y. Nakata M. Bull. Chem. Soc. Jpn. 1998, 71: 1417

Crossref Search in Google Scholar
3c Ichige T. Kamimura S. Mayumi K. Sakamoto Y. Terashita S. Ohteki E. Kanoh N. Nakata M. Tetrahedron Lett. 2005, 46: 1263

Crossref Search in Google Scholar
4a Chen X. Fan C. Xu X. Chin. J. Chem. 2000, 18: 717

Crossref Search in Google Scholar
4b Hong Z. Chen X. Xu X. Tetrahedron Lett. 2003, 44: 485

Crossref Search in Google Scholar
4c Hong Z. Chen X. Xu X. Tetrahedron Lett. 2003, 44: 489

Crossref Search in Google Scholar
4d Gao Y. Nan F. Xu X. Tetrahedron Lett. 2000, 41: 4811

Crossref Search in Google Scholar
4e Liao X. Xu X. Tetrahedron Lett. 2000, 41: 4641

Crossref Search in Google Scholar
4f Liu P. Liao X. Xu X. Chin. J. Chem. 2003, 21: 811

Crossref Search in Google Scholar
4g Liu P. Xu X. Tetrahedron Lett. 2004, 45: 5163

Crossref Search in Google Scholar
5a Dess DB. Martin JC. J. Org. Chem. 1983, 48: 4155

Crossref Search in Google Scholar
5b Dess DB. Martin JC. J. Am. Chem. Soc. 1991, 113: 7277

Crossref Search in Google Scholar
6a Marynoff BE. Reitz AB. Chem. Rev. 1989, 89: 863

Crossref Search in Google Scholar
6b Burri KF. Cardone RA. Chen WY. Rosen P. J. Am. Chem. Soc. 1978, 100: 7069

Crossref Search in Google Scholar
7a Paquette LA. Wang TZ. Philippo C. Wang SP. J. Am. Chem. Soc. 1991, 113: 7277

Crossref Search in Google Scholar
7b Nicolaou KC. Seitz SP. Pavia MR. J. Am. Chem. Soc. 1982, 104: 2030

Crossref Search in Google Scholar
8 Stock G. Nakamura E. J. Org. Chem. 1979, 44: 4010

Crossref Search in Google Scholar
9 Blanchette MA. Choy W. Davis JT. Essenfeld AP. Masamune S. Roush WR. Saka T. Tetrahedron Lett. 1984, 25: 2183

Crossref Search in Google Scholar
13 Gao Y. Klunder JM. Hanson RM. Masamune H. Ko SY. Sharpless KB. J. Am. Chem. Soc. 1987, 109: 5765

Crossref Search in Google Scholar
14a Caron M. Sharpless KB. J. Org. Chem. 1985, 50: 1557

Search in Google Scholar
14b Chong JM. Sharpless KB. J. Org. Chem. 1985, 50: 1560

Search in Google Scholar
15 Payne GB. J. Org. Chem. 1962, 27: 3819

Search in Google Scholar
16 Trost BM. Madsen R. Guile SD. Brown B. J. Am. Chem. Soc. 2000, 122: 5947

Crossref Search in Google Scholar
17a
Compound 20: white solid; mp 80-81 °C; [α]_D ²⁰ -234 (c = 0.40, CHCl₃). IR (film): 2942, 1740, 1376, 1243, 1092, 1033 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 6.27 (d, J = 10.5 Hz, 1 H), 6.05 (dd, J = 8.4 Hz, 2 H), 4.22 (d, J = 7.5 Hz, 1 H), 4.83 (d, J = 7.5 Hz, 1 H), 4.71 (d, J = 7.5 Hz, 1 H), 4.65 (d, J = 12.3 Hz, 1 H), 4.37 (d, J = 12.3 Hz, 1 H), 4.92 (d, J = 7.5 Hz, 1 H), 3.97-4.01 (m, 1 H), 3.73 (d, J = 8.4 Hz, 1 H), 3.40 (s, 3 H), 3.32 (s, 3 H), 2.50-2.62 (m, 1 H), 2.15-2.33 (m, 1 H), 2.14-2.15 (m, 8 H), 2.054 (s, 3 H), 2.047 (s, 3 H), 1.74 (s, 3 H), 1.23 (s, 3 H), 1.21 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 170.6, 170.1, 139.0, 134.6, 126.0, 118.1, 91.0, 90.8, 82.7, 79.9, 75.2, 69.0, 68.4, 65.2, 55.7, 55.2, 40.4, 39.8, 30.3, 24.6, 21.1 (2 C), 21.0, 20.0, 19.9, 18.3. ESI-MS: m/z = 521.3 [M + Na]⁺. HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₆H₄₂O₉: 521.2721; found: 521.2743.
17b
The crystallo-graphic data for 20 has been deposited at the Cambridge Crystallographic Data Centre with deposition no. CCDC 632316.
19 Lombardo L. Org. Synth. 1987, 65: 81

Crossref Search in Google Scholar
20 Takai K. Kakiuchi T. Kataoka Y. Utimoto K. J. Org. Chem. 1994, 59: 2668

Crossref Search in Google Scholar
21 Petasis NA. Bzowej EI. J. Am. Chem. Soc. 1990, 112: 6392

Crossref Search in Google Scholar

10

Compound 15: colorless oil; [α]_D ²⁰ +15.8 (c = 0.50, MeOH). IR (film): 2932, 1717, 1676, 1448, 1184, 1137, 1098, 1037 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 10.09 (d, J = 7.8 Hz, 1 H), 6.14 (s, 1 H), 6.12 (d, J = 7.8 Hz, 1 H), 5.39 (s, 1 H), 5.22 (t, J = 7.5 Hz, 1 H), 4.77 (d, J = 7.2 Hz, 1 H), 4.72 (d, J = 7.2 Hz, 1 H), 4.22 (q, J = 7.2 Hz, 2 H), 4.08-4.11 (m, 1 H), 3.62-3.66 (m, 1 H), 3.39 (s, 3 H), 3.01 (d, J = 7.5 Hz, 2 H), 2.19 (s, 3 H), 1.40-2.10 (m, 8 H), 1.64 (s, 3 H), 1.30 (t, J = 7.2 Hz, 3 H), 1.20 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 191.7, 167.3, 161.6, 139.7, 137.2, 126.2, 124.4, 120.8, 90.7, 77.8, 74.8, 72.67, 60.6, 55.5, 36.0, 31.5, 30.1, 26.5, 24.6, 21.0, 16.1, 14.3, 14.2. ESI-MS: m/z = 409.1 [M + H]⁺, 431.1 [M + Na]⁺. HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₃H₃₆O₆: 431.2404; found: 431.2401.

11

Compound 8: colorless oil; [α]_D ²⁰ +88.4 (c = 0.49, CHCl₃). IR (film): 2979, 2934, 1707, 1448, 1380, 1222, 1145, 1097, 1037, 919 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 6.81 (t, J = 7.2 Hz, 1 H), 5.36 (t, J = 7.5 Hz, 1 H), 4.82 (d, J = 8.1 Hz, 1 H), 4.77 (d, J = 7.5 Hz, 1 H), 4.75 (d, J = 7.5 Hz, 1 H), 4.73 (d, J = 8.1 Hz, 1 H), 4.22 (q, J = 7.2 Hz, 2 H), 3.76-3.80 (m, 1 H), 3.69 (d, J = 5.1 Hz, 1 H), 3.38 (s, 3 H), 3.37 (s, 3 H), 2.70-3.10 (m, 4 H), 2.32-2.40 (m, 1 H), 2.00-2.10 (m, 2 H), 1.80-2.00 (m, 2 H), 1.50-1.70 (m, 3 H), 1.62 (s, 3 H), 1.32 (t, J = 7.2 Hz, 3 H), 1.25 (s, 3 H), 1.19 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 168.0, 142.0, 139.1, 127.8, 123.2, 91.4, 90.9, 79.6, 77.4, 76.4, 75.9, 60.0, 55.6, 55.4, 39.7, 38.4, 33.9, 29.5, 27.7, 23.6, 22.7, 21.4, 15.4, 14.3. ESI-MS: m/z = 463.2 [M + Na]⁺. HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₄H₄₀O₇: 463.2666; found: 463.2685.

12

The stereochemistry of the conjugated double bond is assigned from the chemical shift and the coupling constant data of the vinylic proton, and by analogy with closely related cyclizations.

18

Compound 22: colorless oil; [α]_D ²⁰ -254 (c = 0.10, CHCl₃). IR (film): 2981, 2945, 2855, 1734, 1673, 1647, 1440, 1376, 1275, 1244, 1033, 910 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 6.98 (d, J = 10.2Hz, 1 H), 6.25 (d, J = 11.1 Hz, 1 H), 5.95 (d, J = 10.2 Hz, 1 H), 5.03 (d, J = 7.2 Hz, 1 H), 4.82 (d, J = 7.5 Hz, 1 H), 4.69 (d, J = 7.5 Hz, 1 H), 4.42 (d, J = 7.2 Hz, 1 H), 3.98-4.02 (m, 1 H), 3.70-3.73 (m, 1 H), 3.40 (s, 3 H), 3.33 (s, 3 H), 1.80-2.70 (m, 4 H), 2.27 (s, 3 H), 2.00 (s, 3 H), 1.40-1.80 (m, 6 H), 1.83 (s, 3 H), 1.23 (s, 3 H), 1.20 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 190.2, 170.6, 145.2, 140.7, 131.9, 118.3, 91.1, 91.0, 82.5, 80.1, 75.2, 68.5, 68.4, 55.7, 55.3, 40.2, 39.6, 30.1, 27.5, 24.5, 21.3, 21.0, 20.1, 20.0, 18.8. ESI-MS: m/z = 491.1 [M + Na⁺]. HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₅H₄₀O₈: 491.2615; found: 491.2605.

22

Compound 5: colorless oil; [α]_D ²⁰ -176 (c = 0.05, CHCl₃). IR (film): 2925, 2853, 1742, 1458, 1375, 1240, 1144, 1092, 1072, 1034, 910 cm^-1. ¹H NMR (500 MHz, CDCl₃): δ = 6.08-6.13 (m, 3 H), 4.96 (d, J = 7.4 Hz, 1 H), 4.93 (s, 1 H), 4.85 (s, 1 H), 4.84 (d, J = 7.3 Hz, 1 H), 5.03 (d, J = 7.3 Hz, 1 H), 4.39 (d, J = 7.4 Hz, 1 H), 4.03 (dd, J = 3.0 Hz, 1 H), 3.69 (d, J = 8.3 Hz, 1 H), 3.40 (s, 3 H), 3.33 (s, 3 H), 1.40-2.80 (m, 10 H), 1.98 (s, 3 H), 1.88 (s, 3 H), 1.73 (s, 3 H), 1.25 (s, 3 H), 1.21 (s, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 169.9, 143.5, 137.4, 121.2, 119.0, 113.9, 112.9, 91.1, 91.0, 82.7, 80.2, 75.3, 69.8, 68.3, 55.7, 55.2, 40.3, 39.8, 30.4, 29.7, 24.6, 22.8, 21.5, 21.1, 20.2, 18.4. ESI-MS: m/z = 489.4 [M + Na]⁺. HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₆H₄₂O₇: 489.2828; found: 489.2823.