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Synlett 2003(8): 1155-1159
DOI: 10.1055/s-2003-39899
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Formation of 1-Ethenylcyclopropanols Involving Kulinkovich Cyclo­propanation and Peterson Olefination of α-Trimethylsilylesters

Damien Hazelard, Jean Ollivier, Renée Paugam, Jacques Salaün*
Laboratoire des Carbocycles, UMR 8615, Institut de Chimie Moléculaire et des Matériaux d’Orsay, Université de Paris-Sud, 91405 Orsay, France
Fax: +33(1)69156278; e-Mail: jasalaun@icmo.u-psud.fr;
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Publikationsverlauf

Received 26 April 2003
Publikationsdatum:
11. Juni 2003 (online)

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Abstract

Mercuric iodide catalyzed condensation of bis-silyl­ketene acetals with benzaldehyde provided a 1:1 erythro and threo mixture of α-trimethylsilylesters. Only the threo adducts underwent titanium(IV)-mediated cyclopropanation and acid induced Peterson olefination to provide (Z)-1-ethenylcyclopropanols of considerable synthetic potential.

Key words

condensation - elimination - ring closure - titanium - neighbouring group effect

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  • To a solution of 4 g (11 mmol) of the 1:1 mixture of ethyl 3-phenyl-2-(trimethylsilyl)-3-(trimethylsilyloxy)propionate erythro -6a and threo- 7a in 15 mL of THF containing 0.62 g (2.2 mmol; 0.2 equiv) of Ti(i-PrO)4 was added dropwise a 2.54 M solution of ethylmagnesium bromide (11 mL, 27 mmmol; 2.5 equiv) in diethyl ether within 4 h. The reacting mixture was cooled to 0 °C (iced-water bath), then diluted with diethyl ether and hydrolyzed with 10 mL of aq NH4Cl. After filtration through celite, the separated organic layer was washed with brine, dried on Na2SO4 and concentrated in vacuo. Flash chromatography of the residue (eluant: pentane/diethyl ether 9:1) gave two products:
  • 20a

    1-[2-Phenyl-1-(trimethylsilyl)-2-(trimethylsilyl-oxy)ethyl]cyclopropanol 9a: 1.94 g (52% yield); 1H NMR (250 MHz, CDCl3) δ -0.08 (s, 9 H), 0.71 (d, J = 4.95 Hz, 1 H), 0.25-0.88 (m, 4 H), 3.24 (s, 1 H), 5.33 (d, J = 4.95 Hz, 1 H), 7.19-7.33 (m, 5 H); 13C NMR (66 MHz, CDCl3): δ 0.21, 0.28, 13.27, 15.62, 46.13, 58.92, 78.75, 126, 126.9, 127.9, 144.4; IR 3463, 3379, 2974, 2949 cm-1; MS m/z (EI) 322 (2) [M+], 231 (42), 179 (31), 147 (17), 75 (36), 73 (100), 45 (16); MS m/z (CI with NH3) 340 (0.1), 252 (17), 251 (61), 250 (100), 233 (40), 232 (44), 231 (74) 217 (18), 179 (21), 160 (21), 155 (15), 144 (26), 1433 (100).

  • 20b

    1-(2-Hydroxy-2-phenyl-1-trimethylsilylethyl)cyclo-propanol 9a′: (various amounts 5-10%); white solid: mp 107 °C; 1H NMR (250 MHz, CDCl3) δ -0.07 (s, 9 H), 0.76 (s, 1 H), 0.07-0.97 (m, 4 H), 2.58 (s, 1 H), 3.29 (s, 1 H), 5.44 (s, 1 H), 7.24-7.35 (m, 5 H); 13C NMR (66 MHz, CDCl3) δ 0.32, 13.41, 16.02, 44.86, 59.97, 77.97, 125.17, 126.91, 128.09, 144.41; IR: 3468, 2955, 2898 cm-1; MS m/z (EI) 231 (33), 159 (33), 145 (16), 131 (33), 115 (12), 103 (16), 79 (27), 77 (44), 75 (93), 73 (100), 79 (27), 45 (26); MS m/z (CI with NH3) 251 (19), 250 (81) [M+], 231 (10), 161 (16), 160 (13), 144 (13), 143 (100) 131 (8); Exact mass M+ 250.1377 (calcd for C14H22SiO2 250.1389).

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  • 27 Molecular mechanics calculations (using a MM+ force field) and semi-empirical ZINDO calculations have been performed with the Hyperchem software (version 5.1). The Ti-O and Ti-C bond lengths and the Ti-bond angles were in accord with reported RX data for titanium complexes. See: Gais HJ. Volhardt J. Linder HJ. Paulus H. Angew. Chem., Int. Ed. Engl.  1988,  27:  1541 
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21

Base-induced Peterson olefination of cyclopropanols 9a and 11a led to ring-opened derivatives (see ref. 1).

22

To a stirred solution of 340 mg (1 mmol) of cyclopropanol 9a in 5 mL of methanol at r.t. was added two drops of chlorotrimethylsilane. The reaction was complete within 2 h, as monitored by TLC. Then the solvent was removed in vacuo; flash chromatography of the residue (eluant: pentane/diethyl ether 9:1) gave 128 mg (76% yield) of 1-(Z)-styryl cyclopropanol 12. 1H NMR (250 MHz, CDCl3) δ 0.71-1.32 (m, 4 H), 2.16 (s, 1 H), 5.26 (d, J = 13 Hz, 1 H), 6.53 (d, J = 13 Hz, 1 H), 7.32-7.55 (m, 5 H); MS m/z (EI) 160 (41) [M+], 159 (74), 145 (54), 131 (68), 127 (36), 115 (43), 103 (63), 91 (33), 77 (100), 51 (52); MS m/z (CI with NH3) 178 (100), 161 (22), 160 (17), 159 (14), 143 (18), 131 (13).

26

X-ray crystallographic data of the diol 9a′, will be published in Zeitschrift fuer Kristallographie.