✍ Scribed by Markus E. Scheller; W. Bernd Schweizer; Bruno Frei
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The terms A, B, and C are used for the description of diastereoisomers, whose configurations were not assigned conclusively.
Due to the low amounts of pure 5A + Bin our hands, the oxidation was not repeated with CrO,/pyridine, the reagent which would have led to a higher yield of 2. MHz): -4.7, -2.1 (217, 2 CH,-Si); 17.9, 21.3, 25.9, 27.4 (4y, CH,-CO, CH,-C(3), CH,-C(7), C(8)); 27.2 (4, 3 CH,-C-Si); 22542.6 (21, C(4), C(5)); 65.3 ( I , C(1)); 35.0 (d, C(2)); 124.5 (d, C(6)); 17.7 (s, C-Si); 75.2 (s, C(3)); 131.9 (s, C(7)); 171.0 (s, C=O). MS: 250 (7, M t -H20, CH,COOH), 193 (30), 151 (9), 115 (7), 93 (8), 75 (16), 73 (loo), 69 (21), 59 (28), 43 (lo), 41 (14).
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## Abstract For Abstract see ChemInform Abstract in Full Text.
The synthesis of the cyclopropyl silyl ketones 1 4 is described. The trimethylsilyl ketone 1 was prepared from geraniol ((E)-5) in ca. 10% overall yield by cyclopropanation leading to 6 , Cr03 oxidation to the aldehyde 8, reaction of the latter with trimethylsilyl anion to 14A + B, and CrO? oxidatio
The photolyses and thermolyses of the cc,l(-epoxy silyl ketones 5 and 6 are described. On n,n\*-excitation, the silyl ketones 5 and 6 were transformed to the ketone 7 and the ketene 8 in quantitative yield. The formation of 8 may be explained by initial cleavage of the C(cx-0 bond and subsequent C(l