1.2- Dihydronaphthalene, hydroxylation

Dihydronaphthalene is often used as a model olefin in the study of epoxidation catalysts, and very often gives product epoxides in unusually high ee s. In 1994, Jacobsen discovered in his study on the epoxidation of 1,2-dihydronaphthalene that the ee of the epoxide increases at the expense of the minor enantiomeric epoxide.Further investigation led to the finding that certain epoxides, especially cyclic aromatically conjugated epoxides, undergo kinetic resolution via benzylic hydroxylation up to a krei of 28 (Scheme 1.4.9). 

Boyd, D.R., McMordie, R.A S., Sharma, N.D., Dalton, H., Williams, P. and Jenkins, R.O., Stereospecific benzylic hydroxylation of bicyclic alkenes by Pseudomonas putida isolation of (+)-/ -l-hydroxy-l,2-dihydronaphthalene, an arene hydrate of naphthalene from metabolism of... 

Diels-Alder Reactions. Bp3-OEt2 is used to catalyze and reverse the regiospecificity of some Diels-Alder reactions, e.g. with pen-hydroxylated naphthoquinones, sulfur-containing conpounds, the reaction of 1-substituted trans-1,3-dienes with 2,6-dimethylbenzoquinones, and the reaction of 6-inethoxy-l-vinyl-3,4-dihydronaphthalene with p-quinones. BFs-OEta has a drastic effect on the regioselectivity of the Diels-Alder reaction of quinoline- and isoquinoline-5,8-dione with piperylene, which produces substituted azaanthraquinones. This Lewis acid is the most effective catalyst for the Diels-Alder reaction of furan with methyl acrylate, giving high endo selectivity in the 7-oxabicyclo[2.2.1]heptene product (eq 35). ... 

In 1994, Jacobsen and co-workers demonstrated that stereoseleetive oxidation of benzylic C—H bonds is possible utilizing readily available chiral Mn(salen) complexes.They studied the kinetic resolution of 1,2-dihy-dronaphthalene oxide via an asymmetric C—H bond hydroxylation reaction (Scheme 1.59). During the course of experiments on the asymmetric epoxidation of 1,2-dihydronaphthalene with C24, it was observed that the... 

The hydroxyl group would then remain on position 1, and the nitro group might add to the adjacent position 2, yielding l-hydroxy-2-nitro-l,2-dihydronaphthalene. This unstable intermediate might then evolve into 2-nitronaphthalene upon water elimination. It is possible that the nitration of naphthalene in the presence of HOONO occurs by the electrophilic pathway initiated by species originating from HOONO protonation this pathway prevalently yields 1-nitronapthalene, but also affects the formation rate of 2-nitronaphthalene at pH < 2. 

Naphthalene-1,2-oxide is the obligatory intermediate in the microsomal hydroxyl-ation of naphthalene to 1-naphthol, 2-dihydroxy-1,2-dihydronaphthalene... 

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