Proximity Effects. XIII. Stereochemistry of the cis-Bicyclo[3.3.0]octan-2-ols

Structural effects in solvolytic reactions. 51. Examination of the differences in the behavior of secondary and tertiary U-shaped bicyclic derivatives toward solvolysis

“…The corresponding exo alcohol was prepared by the reaction of the endo tosylate with tetrabutylammonium acetate, followed by the hydrolysis of the exo OAc by a procedure described in the literature. 18 The alcohols were converted to the corresponding tosylates by reaction with ptoluenesulfonyl chloride in the presence of pyridine. The melting points of the tosylates are as follows: 18A, 40-41 °C [lit.…”

“…endo-trimethylene-2-norbornyl, -8-norbornyl, and -9-norbornyl tosylates8 (3,17,18,19, 20), and related systems rivatives except in the case of 2-norbornyl (compare 6 vs. 17, 3 vs. 7, and 8 vs. 18). The exo/endo rate ratios are large for both secondary and tertiary 2-norbornyl derivatives.…”

Proximity Effects. XII. Reaction of cis- and trans-Cycloöctene Oxide with Bases

“…Chromatography on alumina of the mixture of phenylurethans that was formed separated as the major component the phenylurethan of exo-cisbicyclo [3.3.0]octan-2-ol, identified by mixed melting point and comparison of the infrared spectrum with the spectrum of an authentic sample. 8 The minor component was similarly identified as 1,2,8octanetriol tris-phenylurethan.10 Based on this separation, the yields of II and IV from the reaction of <ra»5-cyclooctene oxide with lithium diethylamide are calculated to be 10-15% and 55-60%, respectively.…”

“…A p-nitrobenzoate prepared from the mixture was shown by mixed melting point to be the p-nitrobenzoate of exo-cfs-bicyclo [3.3.0 ]octan-2-ol (IV). 8 Indirect separation of the mixture of II and IV was effected by treatment with phenyl isocyanate to form a mixture of phenylurethans, which was then ozonized. The ozonization product was treated with sodium borohydride and then with phenyl isocyanate.…”

Syntheses and reactions of 3-substituted tricyclo[3.3.0.02,6]octanes and of tricyclo[3.3.0.02,6]oct-3-ene

“…A phenylurethan of this alcohol had the same melting point as that reported for the phenylurethan of 16. 23 The hydrogenated alcohol was oxidized with N-bromosuccinimide, following a procedure the cis fusion of the rings and the position of the oxygen is certain, as is the exo configuration of the alcohol, although a small amount of the endo alcohol might have gone unobserved. The position of the double bond of 15 is assigned on mechanistic grounds and on the basis of the great similarity of the nmr spectra of 14 and 15 in the olefinic proton region.…”