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Synlett 2002(1): 0110-0112
DOI: 10.1055/s-2002-19319
LETTER
© Georg Thieme Verlag Stuttgart · New York

Olefin Cross-Metathesis of Alkenyl Epoxides with Allyl- and Vinyl-trimethylsilane

Peter Langer*, Edith Holtz
Institut für Organische Chemie der Georg-August-Universität Göttingen, Tammannstrasse 2, 37077 Göttingen, Germany
e-Mail: Planger@uni-goettingen.de;
Further Information

Publication History

Received 10 October 2001
Publication Date:
01 February 2007 (online)

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Abstract

The first olefin cross-metathesis reactions of alkenyl epoxides with allyltrimethylsilane and trimethylvinylsilane are reported. The products represent useful synthetic building blocks in Lewis acid mediated cyclization and condensation reactions.

Key words

allylsilanes - catalysis - cyclizations - epoxides - metathesis

    References

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6

Typical Procedure: A CH2Cl2-solution (7 mL) of 1 (126 mg, 1.1 mmol) and 2a (98 mg, 1.0 mmol) was degassed (argon). A CH2Cl2-solution (8 mL) of Grubb’s catalyst (41 mg, 5 mol%) was added and the solution was stirred under reflux for 8 h and at 20 °C for 16 h. The solvent was removed in vacuo and the residue was purified by column chromato-graphy (silica gel, ether/petroleum ether = 1:5) to give 3a (62 mg, 34%) and 4 (41 mg, 49%) as colourless oils. Spectroscopic data of 3a: 1H NMR (CDCl3, 250 MHz):
-0.03, -0.01 (2 × s, 9 H, SiMe3), 1.35-1.70 (m, 4 H, CH2), 2.10-2.20 (m, 2 H, CH2), 2.45-2.55, 2.75-2.80, 2.90-3.00 (3 × m, 3 × 1 H, O-CH, O-CH2), 5.20-5.35, 5.35-5.50 (2 × m, 2 × 1 H, HC=CH). 13C NMR (CDCl3, 62.5 MHz): -2.09, -1.89 (SiMe3), 18.39, 22.53, 23.44, 29.15, 32.55, 32.88 (CH2), 47.09 (OCH2, both isomers), 51.86, 51.94 (O-CH), 125.90, 126.38, 127.01, 127.30. MS (70 eV): m/z = 184 (2) [M+], 169 (1), 155 (1), 129 (9), 115 (12), 73 (100); the exact molecular mass for C10H20OSi m/z = 184.1283 ± 2 mD [M+] was confirmed by HRMS (EI, 70 eV). All new compounds gave satisfactory spectroscopic and analytical and/or high resolution mass data.