Catalytic oxidations using ruthenium porphyrins - Advances in Catalytic Activation of Dioxygen by Metal Complexes - page 59

styrene, and the small isotopic effects determined at the
and at the were considered to be consistent
with the nonstereospecificity of such reactions 208 . The net oxidation of
benzyl alcohol also obeyed the rate law
The insertion of the imido group into alkane C-H bonds occurs
selective at the tertiary centers. For example, with adamantane, N-( 1 -
adamantyl)tosylamide is formed in 52 and 60% yields from
and respectively, under stoichiometric conditions in the
presence of pyrazole 208 . Cyclohexane gave the cyclohexylamide in only 10%
yield; ethylbenzene gave (~80%),
isopropylbenzene yielded (~75%), while
cyclohexene produced 3-( N -tosylamido) cyclohexene (~85%), the insertion
occurring at a C-H bond to an carbon. Formation of a carboradical was
again considered rate-determining for the alkane reactions, with the
relatively large isotope effect being found for tosylamidation of

(Fig. 30) 208 .

cyclohexane by

Application of the more electron deficient complex Ru(TPFPP)CO as a
catalyst for such imido transfer reactions with PhINTs as donor, in the
absence of pyrazole, led to reasonable yields of the corresponding aziridines
and amides 214 . For example, aziridination of allylbenzene, cyclooctene and