Thianthrene as a source of the 1,2-benzene dianion

Synthesis, structure and reactivity of Ni site models of [NiFeSe] hydrogenases

“…A catalytic amount of 4,4′-di-tert-butylbiphenyl was used with two equivalents of lithium powder in tetrahydrofuran at −90 °C to give a radical anion which is strong enough to cleave one of the thianthrene carbon-sulfur bonds. 14 Introduction of elemental selenium into the lithiated product and acidic workup gave the diselenide ('L Se -H') 2 , which can be subsequently reduced with LiAlH 4 to give the selenol 'L Se '-H 2 after acidic workup. Refluxing a solution of 'L Se '-H 2 in tetrahydrofuran with one equivalent of Ni(OCOCH 3 ) 2 •4H 2 O in methanol yields the complex [Ni(L Se )] n as an insoluble black precipitate in 87% yield.…”

“…To the de-oiled Li metal (0.080 g, 11.53 mmol) was added 4,4′-di-tert-butylbiphenyl (DTBB, 0.115 g, 432 µmol) in tetrahydrofuran (3 mL) and the reaction mixture was cooled to −90 °C (acetone-liquid N 2 bath), resulting in the formation of a bright blue solution of a radical anion of DTBB. 14 Thianthrene (1.25 g, 5.76 mmol) in tetrahydrofuran (15 mL) was added at −90 °C and the resulting beige solution was stirred for eight hours during which time the temperature of the reaction mixture was allowed to slowly reach −50 °C. Selenium powder (0.455 g, 5.76 mmol) was added in one batch and the orange solution was allowed to reach room temperature slowly overnight.…”

Applications of metal and non-metal catalysts for the synthesis of oxygen containing five-membered polyheterocylces: a mini review

“…The thianthrene was submitted to reaction as shown in Scheme 28, after reacting with a first carbonyl compound, the lithiation was continued at − 90 to − 78 °C with second carbonyl compound, a second carbonsulfur cleavage occurred to provide organolithium intermediate which was reacted with the electrophile present in the reaction medium to give diols [247][248][249]. These diols were cyclized with 85% phosphoric acid under reflux in toluene to synthesize the substituted phthalans [250].…”

Organodilithium Intermediates as Useful Dianionic Synthons: Recent Advances

“…The DTBB catalyzed monolithiation of 192 can be performed at -90°C to give intermediate 193, which by reaction with a first carbonyl compound as electrophile and further selective reductive cleavage of one of the remaining carbon-sulphur bonds in the highly reductive reaction medium led to a new [101,102]. By applying this methodology, thianthrene could be considered as a 1,2-dilithiobenzene (I) synthetic equivalent.…”