Internal return in the slver ion catalyzed rearrangement of N-chloramines

Sigmatropic Rearrangements and Related Processes Promoted by Silver

“…15 Further studies revealed that the participation of both s and p electrons played an important role in controlling the stereochemistry of such rearrangements. On the other hand, strained s bonds directly interact with silver ions, leading to bond breakage and thus initiating rearrangement.…”

Studies on intramolecular cycloadditions involving 3-oxidopyridinium

“…From ketone (11) (1.43 g, 7.4 mmol) was obtained ll-aza-lOa-hydroxy-8a,lOP,l l-trimethyltricyclo[5.3.1 .O ' *']undecane (13) (1.14 g, 74%) as a colourless gum, v, , , 3 450, 2 940, 1 460, 1340, 1 150, and 935 cm-'; 6,(60 MHz) 1.2-2.1 (13 H, m), 1.3 (3 H, s, 10-Me), 2.45 (3 H, s, NMe), 2.6 (1 H, m, 9-H), and 3.3 (1 H, m, 7-H) (Found: C, 74.5; H, 11.2; N, 6.7. C,,H,,NO requires C, 74.6; H, 11.1; N, 6.7%).…”

Semidiones derived from bicyclic hydrocarbons

“…This was explained (9) on the basis of the equation (15), a^ = /Sp^Cos^e, where # is a constant, pj the spin density at carbon and 0 is the dihedral angle between the C-H bond involved and the p^ orbital in the TT-system. In e, 0 = 90", and one predicts no interaction by this directed mechanism (hyperconjugation), whereas in d, 0 < 90°, and this hydrogen does interact with the unpaired spin.…”

“…In e, 0 = 90", and one predicts no interaction by this directed mechanism (hyperconjugation), whereas in d, 0 < 90°, and this hydrogen does interact with the unpaired spin. Secondly, note that all the j3-hydrogens which interact in these systems, with the exception of the syn-7-hydrogen in This relationship of bonds is very important in both NMR (14,15) and ESR (11,12) couplings and will be utilized many times in this thesis to assign hyperfine splittings. ly with base and oxygen (12), so one must resort to a higher oxidation state such as the diketone or a-hydroxy ketone.…”