[en] Cinnamyl alcohol was converted to 3-phenyl-2-deuteriopropanol and then to the phenyl selenide, which was then ozonized to its selenoxide (S). When S was decomposed in an inert solvent, the product composition of allybenzenes could be directly related to the kinetic deuterium isotope effect as a function of temperature. Results indicate a tunneling pathway of β elimination

[en] The cyclization-induced rearrangement mechanism proposed by Overman to account for nucleophilic catalysis of the thio-Claisen rearrangement has been tested by application of two criteria, viz., the secondary kinetic deuterium isotope effect at the β (side chain) carbon in phenyl allyl sulfide and the substituent rate effect. The results (k/sub H/k/sub D/ = 1.05 and log k/sub xp/k/sub H/ = 0.25 sigma⁺) do not support the mechanism. Instead, they can be construed to support the previously validated mechanism of nucleophilic triggering of sigmatropic rearrangement

[en] Toluene dioxygenase, a multicomponent enzyme system known to oxidize mononuclear aromatic hydrocarbons to cis-dihydrodiols, oxidized indene and indan to 1-indenol and 1-indanol, respectively. In addition, the enzyme catalyzed dioxygen addition to the nonaromatic double bond of indene to form cis-1,2-indandiol. The oxygen atoms in 1-indenol and cis-1,2-indandiol were shown to be derived from molecular oxygen, whereas 70% of the oxygen in 1-indanol was derived from water. All of the isolated products were optically active as demonstrated by ¹⁹F NMR and HPLC discrimination of diastereomeric esters and by chiroptic methods. The high optical purity of (-)-(1R)-indanol (84% enantiomeric excess) and the failure of scavengers of reactive oxygen species to inhibit the monooxygenation reaction supported the contention that monooxygen insertion is mediated by an active-site process. Experiments with 3-[²H] indene indicated that equilibration between C-1 and C-3 occurred prior to the formation of the carbon-oxygen bond to yield 1-indenol. Naphthalene dioxygenase also oxidized indan to 1-indanol, which suggested that benzylic monoxygenation may be typical of this group of dioxygenases