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Synlett 2010(4): 509-513  
DOI: 10.1055/s-0029-1219152
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Probing a Biomimetic Approach to Mycaperoxide B: Hydroperoxidation Studies

Eduarda M. P. Silva, Richard J. Pye, Christine Cardin, Laurence M. Harwood*
Department of Chemistry, University of Reading, Whiteknights, Reading RG6 6AH, UK
Fax: +44(118)3786121; e-Mail: l.m.harwood@reading.ac.uk;
Further Information

Publication History

Received 13 October 2009
Publication Date:
22 December 2009 (online)

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Abstract

Hydroperoxidation studies on a series of alkene substrates demonstrate the introduction of the hydroperoxide functional group into the required position for a biosynthetically inspired synthesis of mycaperoxide B.

Key words

hydroperoxidation - cobalt catalyst - mycaperoxide - ­marine endoperoxide - Michael addition.

    References and Notes

  • 1 Tanaka J. Higa T. Suwanborirux K. Kokpol U. Bernardinelli G. Jefford CW. J. Org. Chem.  1993,  58:  2999 
    CrossrefGoogle Scholar
  • 2 Ovenden SPB. Capon RJ. J. Nat. Prod.  1999,  62:  214 
    CrossrefGoogle Scholar
  • 3 Capon RJ. Eur. J. Org. Chem.  2001,  633 
    Google Scholar
  • 4a Harwood LM. Robertson J. Swallow S. Synlett  1999,  1359 
    Google Scholar
  • 4b Harwood LM. Robertson J. Swallow S. Synlett  1999,  185 
    Google Scholar
  • 5a Isayama S. Mukaiyama T. Chem. Lett.  1989,  573 
    Google Scholar
  • 5b Isayama S. Bull. Chem. Soc. Jpn.  1990,  63:  1305 
    Google Scholar
  • 6 Kato K. Yamada T. Takai T. Inoki S. Isayama S. Bull. Chem. Soc. Jpn.  1990,  63:  179 
    CrossrefGoogle Scholar
  • 7a Tokuyasu T. Masuyama A. Nojima M. McCullough KJ. Kim H.-S. Wataya Y. Tetrahedron  2001,  57:  5979 
    Google Scholar
  • 7b Tokuyasu T. Kunikawa S. Abe M. Masuyama A. Nojima M. Kim H.-S. Begum K. Wataya Y. J. Org. Chem.  2003,  68:  7361 
    Google Scholar
  • 7c Wu J.-M. Kunikawa S. Tokuyasu T. Masuyama A. Nojima M. Kim H.-S. Wataya Y. Tetrahedron  2005,  61:  9961 
    Google Scholar
  • 7d Oh CH. Kim HJ. Wu SH. Won HS. Tetrahedron Lett.  1999,  40:  8391 
    Google Scholar
  • 8 Mori K. Sugai T. Maeda Y. Okazaki T. Noguchi T. Naito H. Tetrahedron  1985,  41:  5307 
    CrossrefGoogle Scholar
  • 9 Ito T. Tokuyasu T. Masuyama A. Nojima M. McCullough KJ. Tetrahedron  2003,  59:  525 
    CrossrefGoogle Scholar
  • 10 Falck JR. Lai J.-Y. Cho S.-D. Yu J. Tetrahedron Lett.  1999,  40:  2903 
    CrossrefGoogle Scholar
  • 11a Bellingham R. Jarowicki K. Kocienski P. Martin V. Synthesis  1996,  285 
    Google Scholar
  • 11b Baudin JB. Hareau G. Julia SA. Ruel O. Tetrahedron Lett.  1991,  32:  1175 
    Google Scholar
  • 11c Baudin JB. Hareau G. Julia SA. Ruel O. Bull. Soc. Chim. Fr.  1993,  130:  336 
    Google Scholar
  • 11d Baudin JB. Hareau G. Julia SA. Lorne R. Ruel O. Bull. Soc. Chim. Fr.  1993,  130:  856 
    Google Scholar
  • 12 Gesson JP. Jacquesy JC. Renoux B. Tetrahedron  1989,  45:  5853 
    CrossrefGoogle Scholar
  • 14 Xu X.-X. Dong H.-Q. Tetrahedron Lett.  1994,  35:  9429 
    CrossrefGoogle Scholar
  • 15a Dussault P. Sahli A. Westermeyer T. J. Org. Chem.  1993,  58:  5469 
    Google Scholar
  • 15b Clark GR. Nikaido MM. Fair CK. Lin J. J. Org. Chem.  1985,  50:  1994 
    Google Scholar
  • 15c Schmid G. Hofheinz W. J. Am. Chem. Soc.  1983,  105:  624 
    Google Scholar
  • 16 Green TW. Wuts PGM. In Protective Groups in Organic Synthesis   Wiley-Interscience; New York: 1981.  p.188 
    Google Scholar
  • 17 Tanemura K. Suzuki T. Horaguchi T. J. Chem. Soc., Chem. Commun.  1992,  979 
    CrossrefGoogle Scholar
  • 18 Sabitha G. Babu RS. Reddy EV. Yadav JS. Chem. Lett.  2000,  1074 
    CrossrefGoogle Scholar
13

Typical Procedure for Hydroperoxidation Reaction
Into a flask flushed with oxygen were added 9,10-trans-1-[3′-methylhex-3′-en-6′-ol]-2α,5,5,9β-tetramethyldecahydro-
naphthalen-1α-ol (19, 53 mg, 0.16 mmol), bis(5,5-dimethyl-1-morpholino-1,2,4-hexanetrionato)cobalt(II) (4 mg, 0.008 mmol) and 1,2-DCE (2 mL), and the flask was again charged with oxygen. Triethylsilane (0.052 mL, 0.32 mmol) and t-BuOOH (2 drops) were added via a 1.0 mL gas-tight syringe, and the resulting green solution was stirred vigorously under an oxygen atmosphere at r.t. After stirring for 2.5 h, the solvent was evaporated under reduced pressure. The residue was purified by flash column chromatography on silica. Elution with hexane-acetone (9:1) gave pure 21 as a colourless oil (20 mg, 30%). IR (thin film): νmax = 3390, 2929, 2869, 1461, 1375, 1051, 1017, 801, 729 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 3.68-3.63 (2 H, m, H-6′), 1.63-1.25 (20 H, m, H 2,3,4,6,7,8,10 and H-1′,2′,4′,5′), 1.15 and 1.14 (3 H, s, 3′-CH3), 0.97 (9 H, t, J = 7.4 Hz, SiCH2CH3), 0.93 and 0.92 (3 H, s, 9-CH3), 0.858 (3 H, d, J = 6.4 Hz, 2-CH3), 0.860 (3 H, s, 5α-CH3), 0.83 (3 H, s, 5β-CH3), 0.67 (6 H, q, J = 7.4 Hz, SiCH2CH3). ¹³C NMR (100 MHz, CDCl3): δ = 84.6 and 84.5 (COOTES), 77.1 (C-1), 63.3 (C-6′), 46.2 (C-10), 43.5 and 43.4 (C-9), 41.8 and 41.7 (C-6), 36.6 and 36.3 (C-2), 33.8 (5α-CH3), 33.3 (C-5), 32.6 (C-1′), 32.55 and 32.46 (C-8), 32.2 and 32.0 (C-4′), 31.5 (C-2′), 27.6 and 27.5 (C-3), 27.21 and 27.17 (C-5′), 22.1 (5β-CH3), 22.0 (3′-CH3), 21.7 (C-4), 18.7 (C-7), 16.6 and 16.43 (2-CH3), 16.36 and 16.2 (9-CH3), 6.8 [Si(CH2CH3)3], 3.9 [Si(CH2CH3)3]. HRMS (CI): m/z calcd for C27H54O4Si [M]+ : 470.3791; found: 470.3800.

19

6′α-[2′′-(1α-Hydroxy-9,10- trans -2α,5,5,9β-tetramethyl-decahydronaphthalen-1-yl)ethyl]-6′β-methyl-1′,2′-dioxan-3′β-ol (23a)
Mp (lit.) 49-50 ˚C. IR (thin film): νmax = 3402, 2930, 2863, 1461, 1451, 1372, 1137, 1088, 989 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 5.26 (1 H, q, J = 4.0 Hz, H-3′), 3.04 (1 H, d, J = 4.0 Hz, OH), 2.07-1.17 (20 H, m, H-4′,5′,1′′,2′′ and H-2,3,4,6,7,8,10), 1.15 (3 H, s, 6′-CH3), 0.87 (3 H, d, J = 8.0 Hz, 2-CH3), 0.87 (3 H, s, 5α-CH3), 0.83 (3 H, s, 5β-CH3). ¹³C NMR (100 MHz, CDCl3): δ = 96.4 (C-3′), 80.9 (C-6′), 77.2 (C-1), 46.3 (C-10), 43.4 (C-9), 41.7 (C-6), 36.5 (C-2), 33.8 (5α-CH3), 33.3 (C-5), 32.1 (C-4′), 31.9 (C-5′), 31.4 (C-2′′), 27.8 (C-8 and C-3), 25.4 (C-1′′), 22.1 (6′-CH3), 22.03 (5β-CH3), 21.7 (C-4), 18.7 (C-7), 16.5 (2-CH3), 16.3 (9-CH3). ESI-HRMS: m/z calcd for C21H38O4Na [M + Na]+ : 377.2662; found: 377.2666.

20

Crystal Data for 23a
C21H38O4, M = 354.51, centered monoclinic, C2, a = 24.384 (3), b = 7.4398 (12), c = 11.0398 Å, V = 2000.5 (5) ų, Z = 4, D = 1.177 g cm-³, F(000) = 784. 2586. Independent reflections were collected on an Oxford Gemini S Ultra Image Plate System. The structures was solved by direct methods and refined on F2 using SHELXL97. Final R = 0.0487, weighted R = 0.1345. These data can be obtained free of charge from The Cambridge Crystallo-graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif quoting deposition no. CCDC 750510.