Reactivity of α-diazo sulfonium salts: rhodium-catalysed ring expansion of indenes to naphthalenes.

In the presence of catalytic amounts of the paddlewheel dirhodium complex Rh2(esp)2, α-diazo dibenzothiophenium salts generate highly electrophilic Rh-coordinated carbenes, which evolve differently depending on their substitution pattern. Keto-moieties directly attached to the azomethinic carbon promote carbene insertion into one of the adjacent C-S bonds, giving rise to highly electrophilic dibenzothiopyrilium salts. This intramolecular pathway is not operative when the carbene carbon bears ester or trifluoromethyl substituents; in fact, these species react with olefins delivering easy to handle cyclopropyl-substituted sulfonium salts. When indenes are the olefins of choice, the initially formed cyclopropyl rings smoothly open with concomitant departure of dibenzothiophene, enabling access to a series of 2-functionalized naphthalenes.

Aza-ortho-Quinone Methide and Its Conjugated Acid: Reactivity, Stability and Acidity.

Aza-o-quinone methides and their conjugated acids are reactive drug metabolites that might react with nucleophilic sites of DNAs and proteins to cause cancer or immune responses, and their reactivity with water is the key information to judge if these metabolites are harmful in living systems. For the first time, aza-o-quinone methide (1) and its conjugated acid (2) are observed by laser flash photolysis, and their reactivity, stability and acidity in water are determined.