Synlett 2006(17): 2830-2832  
DOI: 10.1055/s-2006-950264
LETTER
© Georg Thieme Verlag Stuttgart · New York

Homo-Cope-Type Five-Carbon Ring-Expansion Reaction via Silyl Enol Ether

Chiaki Kuroda*a, Tadashi Ueshinoa, Shigenobu Hondaa, Hideyuki Suzukib
a Department of Chemistry, Rikkyo University, Nishi-Ikebukuro, Toshima-ku, Tokyo 171-8501, Japan
Fax: +81(3)39852396; e-Mail: chkkuroda@grp.rikkyo.ne.jp;
b Research Foundation of Itsuu Laboratory, Tamagawa, Setagaya-ku, Tokyo 158-0094, Japan
Further Information

Publication History

Received 4 August 2006
Publication Date:
09 October 2006 (online)

Abstract

A five-carbon ring-expansion reaction from a cyclohexane derivative fitted with a 3-hydroxy-2-silyloxyprop-1-en-1-yl unit in lieu of one of the C=C double bonds in the Cope rearrangement was studied to synthesize cycloundecanone derivatives. It was found that (E)-triethylsilyl enol ether is necessary for the reaction. The trans-isomer with respect to the cyclohexane ring afforded (2E,8E)-cycloundeca-2,8-dien-1-one, while its cis-isomer afforded (2E,8E)- and (2E,8Z)-isomers in a 1:3 ratio.

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Five-Carbon Ring Expansion: In a 100-mL round-bottomed flask, a solution of 3c (114.4 mg, 0.386 mmol) in anhyd CH2Cl2 (40 mL) was prepared at -60 °C under Ar. To this was added 2,6-lutidine (0.13 mL) and Tf2O (0.1 mL) successively with stirring; stirring was continued for 1 h at the same temperature. A sat. aq solution of NH4Cl was added and the mixture was extracted with CH2Cl2. The organic layer was dried and the solvent was evaporated to afford an oily residue, which was chromatographed on silica gel (3 g; hexane-EtOAc, 95:5) to give 11 (43.7 mg, 69%).

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Compound 11: Oil. IR (neat): 1657 cm-1. 1H NMR (CDCl3): δ = 1.47-1.80 (4 H, m), 2.01-2.10 (2 H, m), 2.21-2.30 (4 H, m), 2.61-2.67 (2 H, m), 5.03 (1 H, dt, J = 15.5, 7.6 Hz, CH=CH), 5.31 (1 H, dt, J = 15.5, 7.7 Hz, CH=CH), 5.90 (1 H, d, J = 16.2 Hz, CH=CHCO), 6.31 (1 H, dt, J = 16.2, 7.5 Hz, CH=CHCO). 13C NMR (CDCl3): δ = 27.28, 28.53, 30.07, 34.21, 34.45, 38.59, 128.81, 132.01, 137.38, 156.96, 202.88. HRMS: m/z calcd for C11H16O (M+): 164.1201; found: 164.1235.

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Compound 19: Oil. IR (neat): 1672 cm-1. 1H NMR (CDCl3): δ =1.64-1.74 (4 H, m), 2.17-2.31 (6 H, m), 2.53-2.57 (2 H, m), 5.36-5.43 (1 H, m, CH=CH), 5.52 (1 H, ddt, J = 10.5, 8.2, 1.7 Hz, CH=CH), 6.19 (1 H, dt, J = 16.2, 1.5 Hz, CH=CHCO), 6.80 (1 H, dt, J = 16.2, 6.7 Hz, CH=CHCO). 13C NMR (CDCl3): δ = 22.92, 25.10, 25.15, 28.50, 32.10, 39.81, 128.81, 129.73, 131.57, 151.11, 203.56. HRMS: m/z calcd for C11H16O (M+): 164.1201; found: 164.1221.