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Synlett 2012; 23(14): 2129-2131
DOI: 10.1055/s-0032-1316580
letter
© Georg Thieme Verlag Stuttgart · New York

Total Synthesis of (+)-Cryptocaryanone A

Bingbin Zhang
a   State Key Laboratory of Applied Organic Chemistry, Department of Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China, Fax: +86(931)8912582   eMail: shexg@lzu.edu.cn   eMail: xiexg@lzu.edu.cn
,
Zhen Yang
a   State Key Laboratory of Applied Organic Chemistry, Department of Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China, Fax: +86(931)8912582   eMail: shexg@lzu.edu.cn   eMail: xiexg@lzu.edu.cn
,
Juan Yang
a   State Key Laboratory of Applied Organic Chemistry, Department of Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China, Fax: +86(931)8912582   eMail: shexg@lzu.edu.cn   eMail: xiexg@lzu.edu.cn
,
Gaoyuan Zhao
a   State Key Laboratory of Applied Organic Chemistry, Department of Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China, Fax: +86(931)8912582   eMail: shexg@lzu.edu.cn   eMail: xiexg@lzu.edu.cn
,
Bin Ma
a   State Key Laboratory of Applied Organic Chemistry, Department of Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China, Fax: +86(931)8912582   eMail: shexg@lzu.edu.cn   eMail: xiexg@lzu.edu.cn
,
Xingang Xie*
a   State Key Laboratory of Applied Organic Chemistry, Department of Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China, Fax: +86(931)8912582   eMail: shexg@lzu.edu.cn   eMail: xiexg@lzu.edu.cn
,
Xuegong She*
a   State Key Laboratory of Applied Organic Chemistry, Department of Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China, Fax: +86(931)8912582   eMail: shexg@lzu.edu.cn   eMail: xiexg@lzu.edu.cn
b   State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. of China
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Publikationsverlauf

Received: 07. Mai 2012

Accepted after revision: 27. Mai 2012

Publikationsdatum:
04. Juli 2012 (online)

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Abstract

The first total synthesis of (+)-cryptocaryanone A is described. The synthesis features a Mukaiyama aldol reaction, one-pot saponification/lactonization sequences, and TsOH-assisted dihydropyrone formation as key steps.

Key words

total synthesis - natural products - aldol reaction - saponification - lactonization

Supporting Information

    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
  • Supporting Information
 

  • References and Notes

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  • 12 7-epi-Cryptochinone F (16): [α] d 20 +40 (c = 1.0, CHCl3); 1H NMR (400 MHz, CDCl3): δ = 2.35 (dd, J = 18.0, 5.2 Hz, 1 H), 2.50 (dd, J = 18.4, 5.6 Hz, 1 H), 2.71 (dd, J = 17.0, 3.4 Hz, 1 H), 2.76 (dd, J = 19.8, 3.8 Hz, 1 H), 2.92 (dd, J = 16.8, 13.6 Hz, 1 H), 3.03 (dd, J = 18.2, 8.6 Hz, 1 H), 3.47 (s, 3 H), 3.61 (br dd, J = 14.4, 6.4 Hz, 1 H), 3.83 (br dd, J = 10.6, 5.4 Hz, 1 H), 4.67 (t, J = 6.6 Hz, 1 H), 5.48 (dd, J = 13.2, 3.6 Hz, 1 H), 7.37–7.43 (m, 5 H). 13C NMR (100 MHz, CDCl3): δ = 30.24, 32.05, 34.89, 43.01, 58.18, 74.75, 78.26, 80.94, 110.75, 126.27, 129.11, 129.24, 137.88, 167.88, 176.16, 190.80. IR (KBr): 2985, 2547, 2256, 1739, 1374, 1245, 915, 734 cm–1; HRMS (ESI): m/z [M + H]+ calcd for C18H19O5 +: 315.1227; found: 315.1223
  • 13 Cryptochinone F was isolated from the evergreen tree Cryptocarya chinensis by Chou et al. (see ref. 3)
  • 14 Cryptocaryanone A (1): To a solution of diketone 17 (9 mg, 0.022 mmol) in CH2Cl2 (5 mL) at r.t., was added TsOH·H2O (41 mg, 0.22 mmol). The reaction mixture was stirred for 3 days, then quenched with sat. aq NaHCO3 (2 mL). The layers were separated and the aqueous phase was extracted with CH2Cl2 (3 × 5 mL), dried over anhydrous Na2SO4, filtered, and concentrated. Flash chromatography (hexanes–EtOAc, 3:1) afforded cryptocaryanone A (1; 3 mg, 49%) as a white powder. [α] d 20 +217 (c = 1.0, CHCl3); 1H NMR (400 MHz, CDCl3): δ = 2.41 (dd, J = 17.9, 10.5 Hz, 1 H), 2.73 (dd, J = 16.8, 3.6 Hz, 1 H), 2.94 (dd, J = 17.2, 14.0 Hz, 1 H), 2.99 (dd, J = 18.0, 9.2 Hz, 1 H), 3.88 (dd, J = 19.8, 10.4 Hz, 1 H), 5.46–5.50 (m, 2 H), 6.10 (dd, J = 10.1, 1.8 Hz, 1 H), 6.29 (dd, J = 10.1, 2.7 Hz, 1 H), 7.41–7.45 (m, 5 H); 13C NMR (100 MHz, CDCl3): δ = 30.75, 33.34, 42.94, 76.70, 81.08, 109.00, 124.30, 126.36, 129.13, 129.34, 134.87, 137.71, 162.77, 175.58, 190.47. IR (KBr): 2923, 2253, 1782, 1652, 1589, 1428, 910 cm–1; HRMS (ESI): m/z [M + H]+ calcd for C18H19O5 +: 283.0965; found: 283.0959