Download PDF
Synlett 2004(9): 1513-1516  
DOI: 10.1055/s-2004-829087
LETTER
© Georg Thieme Verlag Stuttgart · New York

Methylsulfonyl and Hydroxyl Substituents Induce Z-Stereocontrol in the McMurry Olefination Reaction

Md. Jashim Uddin, P. N. P. Rao, Edward E. Knaus*
Faculty of Pharmacy and Pharmaceutical Sciences, University of Alberta, Edmonton, Alberta, T6G 2N8, Canada
Fax: +1(780)4921217; e-Mail: eknaus@pharmacy.ualberta.ca;
Further Information

Publication History

Received 3 February 2004
Publication Date:
29 June 2004 (online)

    Permissions and Reprints All articles of this category

Abstract

Aryl ketones possessing methylsulfonyl and hydroxyl substituents, that induce stereocontrol, selectively afford Z-olefins using a Zn-TiCl4 catalyzed McMurry reaction.

Key words

McMurry olefination - stereocontrol - Z-olefins - acetylation

    References

  • 1 McMurry JE. Chem. Rev.  1989,  89:  1513 
    CrossrefGoogle Scholar
  • 2 Corey EJ. Danheiser RL. Chandrasekaran S. J. Org. Chem.  1976,  41:  260 
    CrossrefGoogle Scholar
  • 3 McMurry JE. Krepski LR. J. Org. Chem.  1976,  41:  3929 
    CrossrefGoogle Scholar
  • 4 McMurry JE. Fleming MP. Kees KL. Krepski LR. J. Org. Chem.  1978,  43:  3255 
    Google Scholar
  • 5 Dams R. Malinowski M. Westdrop I. Geise HY. J. Org. Chem.  1982,  47:  248 
    Google Scholar
  • 6 Coe PL. Scriven CE. J. Chem. Soc., Perkin Trans. 1  1986,  475 
    CrossrefGoogle Scholar
  • 7a Gauthier S. Sancéau J.-Y. Mailhot J. Caron B. Cloutier J. Tetrahedron  2000,  56:  703 
    CrossrefGoogle Scholar
  • 7b Detsi A. Koufaki M. Calogeropoulou T. J. Org. Chem.  2002,  67:  4608 
    CrossrefGoogle Scholar
  • 8 Habeeb AG. Rao PNP. Knaus EE. J. Med. Chem.  2001,  44:  3039 
    CrossrefPubMedGoogle Scholar
  • 9 Rahim MA. Rao PNP. Knaus EE. Bioorg. Med. Chem. Lett.  2002,  12:  2753 
    CrossrefGoogle Scholar
  • 10 Rao PNP. Amini M. Li H. Habbeb AG. Knaus EE. J. Med. Chem.  2003,  46:  4872 
    CrossrefGoogle Scholar
  • 11 Uddin MJ. Rao PNP. Knaus EE. Bioorg. Med. Chem. Lett.  2004,  14:  1953 
    CrossrefGoogle Scholar
  • 12 Huang H.-C. Li JJ. Garland DJ. Chamberlain TS. Reinhard EJ. Manning RE. Seibert K. Koboldt CM. Gregory SA. Anderson GD. Veenhuizen AW. Zhang Y. Perkins WE. Burton EG. Cogburn JN. Isakson PC. Reitz DB. J. Med. Chem.  1996,  39:  253 
    CrossrefGoogle Scholar
  • 13 Buu-Hoi NP. Hoan N. J. Org. Chem.  1952,  17:  350 
    Google Scholar
  • 14a Fringuelli F. Pellegrino R. Piermatti O. Pizzo F. Synth. Commun.  1994,  18:  2665 
    CrossrefGoogle Scholar
  • 14b Habeeb AG. Rao PNP. Knaus EE. J. Med. Chem.  2001,  44:  2921 
    CrossrefGoogle Scholar
  • 14c

    General Procedure for the Synthesis of Compounds 1. Synthesis of 4-(Methylsulfonyl)butyrophenone (1, R ¹ = SO 2 Me, R ² = n -Pr): A solution of Oxone® (potassium peroxymonosulfate) (4.06 g, 6.6 mmol) in H2O (20 mL) was added to a stirred solution of 4-(methylthio)butyrophenone [13] (0.64 g, 3.3 mmol) in 50% THF-MeOH (1:1, v/v; 10 mL) at 0 °C, and the reaction mixture was stirred for 15 h at 25 °C. The solvent was removed in vacuo, H2O (20 mL) was added to the residue, and the mixture was extracted with EtOAc (3 × 30 mL). The combined EtOAc extracts were washed with H2O, the EtOAc fraction was dried (Na2SO4), and the solvent was removed in vacuo to afford a white solid which was purified by recrystallization from CH2Cl2 n-hexane (1:9, v/v) to afford 1 (R1 = SO2Me, R2 = n-Pr) in 89% yield as white needles; mp 86-88 °C. IR (film): 1148, 1313 (SO2), 1698 (C=O) cm-1. 1H NMR (300 MHz, CDCl3): δ = 1.02 (t, 3 H, J = 7.3 Hz, CH 3), 1.73-1.85 (m, 2 H, CH 2), 2.90 (t, 2 H, J = 7.0 Hz, COCH 2), 3.09 (s, 3 H, SO2CH 3), 8.04 (d, 2 H, J = 8.5 Hz, 4-methylsulfonylphenyl H-2, H-6), 8.13 (d, 2 H, J = 8.5 Hz, 4-methylsulfonylphenyl H-3, H-5). Anal. Calcd for C11H14O3S·1/6H2O: C, 57.61; H, 6.25. Found: C, 57.89; H, 6.25.
    Crossref
  • 15 Rubin VN. Ruenitz PC. Boudinot FD. Boyd JL. Bioorg. Med. Chem.  2001,  9:  1579 
    Google Scholar
  • 16 Strazzolini P. Verardo G. Giumanini AG. J. Org. Chem.  1988,  53:  3321 
    Google Scholar
17

General Procedure for Synthesis of Compounds 4. Synthesis of (Z)-1-(4-acetoxyphenyl)-1-phenyl-2-(4-methylsulfonylphenyl)pent-1-ene [(Z)-4l]: TiCl4 (1.83 mL, 13 mmol) was added drop wise to a stirred suspension of Zn powder (1.7 g, 26.5 mmol) in dry THF (30 mL) under argon at -10 °C, and this mixture was refluxed for 2 h. A solution of 4-(methylsulfonyl)butyrophenone (1, R1 = SO2Me, R2 = n-Pr) (0.75 g, 3.3 mmol) and 4-hydroxybenzophenone (2, R3 = 4-hydroxyphenyl, R4 = Ph) (0.66 g, 3.3 mmol) in THF (65 mL) was added to the cooled suspension of the titanium reagent at 0 °C, and the reaction mixture was refluxed for 2.5 h. After cooling to 25 °C, the reaction mixture was poured into a 10% aq K2CO3 solution (100 mL), vigorous stirring was maintained for 5 min, and the dispersed insoluble material was removed by vacuum filtration using Celite 545. The organic layer was separated and the aqueous layer was extracted with EtOAc (3 × 50 mL). The combined EtOAc extracts were dried (Na2SO4), the solvent was removed in vacuo to afford the olefinic intermediate 3 (R1 = SO2Me, R2 = n-Pr, R3 = 4-hydroxy-phenyl, R4 = Ph), which was dissolved in Et2O (10 mL), and Et3N (0.5 g, 5.0 mmol) was added. Acetyl chloride (0.39 g, 5.0 mmol) was added drop wise at 0 °C, and the reaction was allowed to proceed for 1.5 h at 25 °C with stirring prior to quenching with H2O (20 mL). The organic layer was separated, the aqueous layer was extracted with EtOAc (3 × 30 mL), the combined organic fractions were washed with H2O, and the organic fraction was dried (Na2SO4). Removal of the solvent in vacuo gave a solid that was purified by flash silica gel column chromatography using n-hexaneEtOAc (3:1, v/v) as eluant to afford (Z)-4l (R = n-Pr) as colorless crystals (0.97 g, 68%); mp 132-134 °C. IR (film): 1142, 1322 (SO2), 1585 (C=C), 1757 (C=O of OAc) cm-1. 1H NMR (300 MHz, CDCl3): δ = 0.82 (t, 3 H, J = 7.3 Hz, CH2CH 3), 1.25-1.40 (m, 2 H, CH 2CH3), 2.23 (s, 3 H, OCOCH 3), 2.44 (t, 2 H, J = 7.9 Hz, C=C-CH 2), 3.04 (s, 3 H, SO2CH 3), 6.76 (d, 2 H, J = 8.5 Hz, 4-acetoxyphenyl H-3,
H-5), 6.85 (d, 2 H, J = 8.5 Hz, 4-acetoxyphenyl H-2, H-6), 7.20-7.40 (m, 7 H, phenyl hydrogens, and 4-methylsulfonyl-phenyl H-2, H-6), 7.74 (d, 2 H, J = 8.5 Hz, 4-methyl-sulfonylphenyl H-3, H-5). 13C NMR (75 MHz, CDCl3):
δ = 14.10 (CH2CH2 CH3), 17.77 (CH3C=O), 21.16 (CH2 CH2CH3), 37.64 (CH2CH2CH3), 44.53 (SO2 CH3), 120.69, 126.99, 127.11, 128.26, 129.23, 130.44, 131.46 (Carom-H), 138.03, 139.44, 139.53, 140.53, 142.22, 148.64, 148.96 (Carom-C, Colefin-C, Carom-O, Carom-S), 169.00 (CH3 C=O). Anal. Calcd for C26H26O4S: C, 71.86; H, 6.03; S, 7.38. Found: C, 71.74; H, 5.96; S, 7.27.

18

Crystal data for (Z)-4l: Molecular formula: C26H26O4S, formula weight: 434.53, crystal system: monoclinic, space group: P21/c(14) with unit cell dimensions a = 8.0403 (6) Å, b = 14.5485 (12) Å, c = 19.9285 (16) Å, β = 101.4182 (15)º, V = 2285.0 (3) Å3, Z = 4, = 1.263 gcm-3, µ = 0.171 mm-1. A crystal fragment of approximate dimensions(mm3) 0.73 × 0.40 × 0.04 was mounted in a nonspecific orientation on Bruker PLATFORM/SMART 1000 CCD diffractometer. All intensity measurements were performed using Mo Kα radiation (λ = 0.71073 Å) with a graphite crystal incident beam monochromator. The intensity data were collected at -80 °C using an ω scan (0.3º) (10 s exposures). A total 4675 independent reflections were collected to a maximum 2θ limit at 52.9°. The structure was solved by direct methods. Refinement of atomic parameters was carried out by using full-matrix least-squares on F2 (SHELXL-93), giving final agreement factor (R indices) of R1 = 0.0484 and wR2 = 0.1116. Crystallographic data (excluding structure factors) have been deposited at the Cambridge Crystallographic Data Centre as supplementary publication number CCDC 228635. Copies of the data can be obtained free of charge by application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: 44(1223)336033 or e-mail: deposit@ccdc.cam.ac.uk).