Sulfur-oxygen bond cleavage of secondary and tertiary -toluenesulfonates under nucleophilic solvolytic conditions

Solvolysis of vinyl triflates. Effect of alkyl substituents, solvents, and added nucleophiles

“…Preparative gas chromatography was performed on a Varían Aerograph Model 90-Pgas chromatograph using the following columns: A, 0.375 in. X 15 ft 20% Carbowax 20M on [45][46][47][48][49][50][51][52][53][54][55][56][57][58][59][60]B,0.375 Chromosorb W. Analytical gas chromatography was performed on a Varían Aerograph Model 1520 or a Perkin-Elmer Model 810 instrument equipped with flame ionization detector using the following columns: F, 0.125 in. X 10 ft 10% Carbowax 20M on 80-100 Chromosorb W; G, 0.125 in.…”

The Synthesis and Reactions of Yomogi Alcohol. Conversion of the artemisyl skeleton to the santolinyl skeleton by a 1,2‐shift of a vinyl group. Synthesis of santolinatriene

“…Photo-oxygenation of 2,5,5-triinethyl-hept-2-ene (11) was carried out cxactly as clcscribed in the preparation of yoniogi alcohol (above) ; 21 g of hydrocarbon gave a practically quantitativc yield of 12 with 13, which were separately obtained pure by distillation. (26). 0.75 g 2,2,5,5-tetramethyl-4vinyl-tetrahydrofuran-3-cis-01 was acetylated in 2 1111 of dry pyridine with 2 g of acetic anhydride at 40" for 24 h, the mixture decomposed with ice water, the product extracted with ether, and thc organic phase washed with dilute sulfuric acid, water, sodium hydrogencarbonate solution and finally water.…”

“…Another attempt to invert the 3-configuration was made by treating the alcohol 48 (R = H) with thionyl chloride in pyridine. The resulting mixture of sulfites (50) was then heated with sodium acetate in ethanol when, again in analogy with Gassman's observations [26], the major product arose by S-0 bond cleavage, and proved to be once more the unchanged oxetan alcohol 48 (R = H), although small amounts of one of the possible 3-ethoxyoxetans 48 (R = C,H,), probably of the same stereochemistry as the starting material, were observed, together with some 2,5,5-trimethyl-3,4-dihydroxy-hepta-3,4-diene (51) of unknown stereochem-istry9).…”

The Rearrangement Route to 3-CH2X-2-azabicyclo[2.1.1]hexanes. Substituent Control of Neighboring Group Participation

“…An initially formed bromonium ion, 3 , might be attacked by the oxygen atom on the methylene group to give a five-membered ring oxonium ion, 7 . If the group R on the oxonium ion 7 is attacked by water (path a), the tricycle 4 is formed (entries 1−2, 4−5) . If the R group on oxonium ion 7 is not labile, preferential attack of water at the methylene (path b) results in migration of the OR group from methylene to C 5 , as observed in the formation of structure 5 by aryloxy migration (entry 3).…”