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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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Publication History

Received 26 April 2003
Publication Date:
11 June 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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  • 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).

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  • 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.