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Synlett 2006(16): 2577-2580  
DOI: 10.1055/s-2006-951474
LETTER
© Georg Thieme Verlag Stuttgart · New York

Peterson Allenation Using (Z)-(1-Lithio-1-alkenyl)trimethylsilanes

Akira Tsubouchi, Takashiro Kira, Takeshi Takeda*
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan
Fax: +81(42)3887034; e-Mail: takeda-t@cc.tuat.ac.jp;
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Publication History

Received 5 July 2006
Publication Date:
22 September 2006 (online)

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Abstract

Lithium alkoxides of β-silylallylic alcohols underwent the Peterson elimination in DMF to give allenes. Allenes were also directly obtained by a Peterson allenation reaction from carbonyl compounds using (Z)-(1-lithio-1-alkenyl)trimethylsilanes in one pot.

Key words

alcohols - allenes - carbonyl - elimination - silicon

    References and Notes

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8

Typical Procedure for the Preparation of Allenes 2 from ( Z )-β-Silylallylic Alcohols 1: n-BuLi (1.6 M in hexane, 0.23 mL, 0.37 mmol) was added dropwise to an Et2O solution (0.9 mL) of 1d (97 mg, 0.30 mmol) at 0 °C under argon. After 15 min, DMF (4.2 mL) was added in one portion, and the mixture was warmed to 50 °C and stirred for 3 h. The reaction was quenched by addition of H2O and the products were extracted into Et2O. The organic layer was washed with H2O and dried (Na2SO4). The solvent was concentrated under reduced pressure and the crude product was purified by PTLC (hexane-EtOAc, 98:2) to give 2d (63 mg, 90%). IR (neat): 3061, 3027, 2921, 2852, 1955, 1602, 1496, 1453, 847, 750, 698 cm-1; 1H NMR (300 MHz, CDCl3): δ = 2.68-2.85 (m, 5 H), 4.66 (d, J = 7.1 Hz, 2 H), 5.07-5.15 (m, 1 H), 7.20-7.38 (m, 10 H); 13C NMR (75 MHz, CDCl3): δ = 40.9, 41.8, 75.8, 93.1, 125.9, 128.1, 129.2, 140.4, 207.9; Anal. Calcd for C18H18: C, 92.26; H, 7.74. Found: C, 92.06; H, 8.02.

10

Typical Procedure for the Allenation of Carbonyl Compounds 7: A solution of 9c (115 mg, 0.45 mmol) in Et2O (0.6 mL) was placed in a flask under argon and t-BuLi (1.5 M in pentane, 0.35 mL, 0.53 mmol) was added dropwise at -78 °C. After stirring for 2 h at -78 °C, a solution of 7a (72 mg, 0.30 mmol) in Et2O (0.3 mL) was added dropwise. The mixture was slowly warmed to 0 °C and DMF (4.2 mL) was added in one portion. The mixture was heated at 50 °C for 2 h, and the reaction was quenched by addition of H2O. The usual work-up and purification gave 2h (89 mg, 91%). IR (neat): 3061, 3027, 2921, 1947, 1601, 1496, 1453, 745, 694 cm-1; 1H NMR (300 MHz, CDCl3): δ = 2.35-2.54 (m, 4 H), 2.73-2.88 (m, 4 H), 6.18 (quin, J = 3.0 Hz, 1 H), 7.11-7.30 (m, 15 H); 13C NMR (75 MHz, CDCl3): δ = 33.9, 34.6, 96.5, 107.5, 125.8, 126.48, 126.53, 128.3, 128.40, 128.44, 135.5, 141.9, 202.4; Anal. Calcd for C25H24: C, 92.54; H, 7.46. Found: C, 92.28; H, 7.59.

13

A similar reaction of 3-phenylpropanal with 1-lithio-1-(trimethylsilyl)-1-octene, prepared from the corresponding iodide 10d by treatment with tert-butyllithium, [9a] gave 2a in 8% yield and the protodesilylation product, 1-phenyl-4-undecen-3-ol, was isolated in 66% yield. The Peterson elimination of 1a in the presence of lithium iodide gave 2a in only 18% yield. Decrease of the yield might, therefore, be attributable to iodide ion generated by the lithium-halogen exchange.