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Synlett 2012(3): 458-462  
DOI: 10.1055/s-0031-1290324
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

TIPSOTf-Promoted Tandem Reaction through Rearrangement of Epoxides into Aldehydes with Selective Alkyl Migration Followed by Prins-Type Cyclization to Cyclopentanes

Takeshi Kodama, Shingo Harada, Takeshi Tanaka, Yoshimitsu Tachi, Yoshiki Morimoto*
Department of Chemistry, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan
Fax: +81(6)66052522; e-Mail: morimoto@sci.osaka-cu.ac.jp;
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Publication History

Received 14 November 2011
Publication Date:
27 January 2012 (online)

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Abstract

The tandem reaction of trisubstituted epoxides to cyclopentanes promoted by TIPSOTf in nitromethane has been found. It consists of stereospecific rearrangement of epoxides into aldehydes accompanied with selective alkyl migration and subsequent Prins-type cyclization of the aldehydes generated to cyclopentanes.

Key words

cyclization - epoxides - rearrangement - steric hindrance - tandem reaction

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9

Typical Procedure for the Tandem Reaction: To a solution of epoxide 7b (R¹ = TMS, 30.0 mg, 0.100 mmol), prepared from 7a (R¹ = H, ref. 8) according to footnote d in Table  [¹] , in nitromethane (1.0 mL) were successively added dropwise 2,6-lutidine (92 µL, 0.703 mmol) and triisopropyl-silyl triflate (0.135 mL, 0.502 mmol) under a nitrogen atmosphere at 0 ˚C, and the mixture was stirred at the same temperature for 45 min. H2O was added to the solution, and the aqueous layer was extracted with hexane. The organic layer was washed with brine, dried over anhyd Na2SO4, and concentrated under reduced pressure. The residue was purified by flash column chromatography (hexane-benzene, 98:2) on silica gel to afford a mixture of cyclopentanes 12a and 12b (29.4 mg, 64% yield) in a ratio of 3.2:1 as a colorless oil; R f 0.58 (hexane-benzene, 95:5). ¹H NMR (400 MHz, CDCl3): δ = 4.77 (s, 1 H), 4.71 (s, 1 H), 3.88 (d, J = 6.6 Hz, 0.24 H), 3.82 (d, J = 7.3 Hz, 0.76 H), 2.53-2.64 (m, 1 H), 1.14-1.93 (m, 8 H), 1.72 (s, 3 H), 1.22 (s, 1.44 H), 1.20 (s, 4.56 H), 0.97-1.12 (m, 21 H), 0.94 (s, 0.72 H), 0.90 (s, 2.28 H), 0.10 (s, 9 H). ¹³C NMR (75 MHz, CDCl3): δ = 147.3, 147.2, 111.1, 110.7, 84.1, 77.2, 74.0, 54.8, 53.7, 45.6, 45.4, 39.9, 39.4, 35.3, 34.8, 34.2, 29.8, 26.7, 24.1, 20.0, 19.7, 18.6, 18.5, 18.4, 13.4, 13.3, 2.7, 2.6. IR (neat): 3076, 1641, 1462, 1378, 1107, 882 cm-¹. HRMS (FAB): m/z [M - H+] calcd for C26H53O2Si2: 453.3584; found: 453.3591.

11

Compound 16a: R f = 0.62 (hexane). ¹H NMR (400 MHz, CDCl3): δ = 4.77-4.81 (m, 1 H), 4.68-4.72 (m, 1 H), 4.24 (d, J = 7.3 Hz, 1 H), 3.44 (d, J = 9.5 Hz, 1 H), 3.30 (d, J = 9.8 Hz, 1 H), 2.59 (dt, J = 9.9, 7.1 Hz, 1 H), 1.82-1.93 (m, 1 H), 1.74 (dt, J = 12.2, 8.4 Hz, 1 H), 1.72 (s, 3 H), 1.32-1.42 (m, 1 H), 1.27 (ddd, J = 12.4, 7.9, 4.6 Hz, 1 H), 1.00-1.09 (m, 21 H), 0.90 (s, 9 H), 0.88 (s, 3 H), 0.03 (s, 3 H), 0.02 (s, 3 H). ¹³C NMR (75 MHz, CDCl3): δ = 147.3, 111.0, 77.3, 67.6, 54.2, 48.0, 32.6, 26.8, 25.9, 19.6, 18.4, 18.3, 17.9, 13.3, -5.5, -5.6. IR (neat): 3079, 1644, 1463, 1254, 1087, 835 cm-¹. HRMS (FAB): m/z [M+] calcd for C25H52O2Si2: 440.3506; found: 440.3515.
Compound 16b: R f 0.51 (hexane). ¹H NMR (400 MHz, CDCl3): δ = 4.74-4.78 (m, 1 H), 4.70-4.74 (m, 1 H), 3.97 (d, J = 7.1 Hz, 1 H), 3.63 (d, J = 10.0 Hz, 1 H), 3.50 (d, J = 10.0 Hz, 1 H), 2.63 (dt, J = 9.3, 7.0 Hz, 1 H), 1.81-1.94 (m, 2 H), 1.72 (s, 3 H), 1.32-1.44 (m, 1 H), 1.18-1.31 (m, 1 H), 0.97-1.10 (m, 21 H), 1.02 (s, 3 H), 0.90 (s, 9 H), 0.04 (s, 3 H), 0.03 (s, 3 H). ¹³C NMR (75 MHz, CDCl3): δ = 147.2, 110.9, 83.9, 66.5, 55.3, 48.0, 33.1, 27.3, 26.0, 22.9, 19.9, 18.39, 18.37, 18.32, 13.2, -5.45, -5.49. IR (neat): 3079, 1642, 1463, 1086, 835 cm-¹. HRMS (FAB): m/z [M - H+] calcd for C25H51O2Si2: 439.3427; found: 439.3422.