Asymmetric dihydroxylation of C,C double bonds using catalytic amounts of osmium tetroxide, selenides, and air

Abstract

Selenides, selenoxides, osmium tetroxide, and potassium osmate dihydrate are in equilibrium in aqueous tert-butanol containing potassium carbonate. We took advantage of this feature to withdraw the equilibrium in each of the two directions to produce allylalcohols from allylselenides and diols from olefins. The latter reaction performed in the presence of catalytic amounts of Cinchona alkaloids and osmium tetroxide allows the enantioselective dihydroxylation of C,C double bonds.

Enantioselective Diamination of Alkenes by Use of a Bisimidoosmium Reagent with the Aid of Chiral Catalysts

“…A review of the literature for previous investigations into the coexistence of related osmium tetroxide and metal ions provided surprisingly few data: it appears that this subject remains limited to the seminal work by Krief on the reversible oxo transfer between osmium and selenium. [24] In the current case it became obvious that usually successful catalysts such as copper and tin readily reacted with 3 and led to partial or complete degradation of the osmium oxidant. Hence, priority was given to metal candidates in their highest oxidation states.…”

2-Azabicyclo[2.2.1]hept-5-en-3-one: Chemical Profile of a Versatile Synthetic Building Block and its Impact on the Development of Therapeutics

“…Our initial studies included the dihydroxylation of Vince lactam by the catalytic use of OsO 4 ( 88 , Scheme ). , N –Mehtylmorpholine N –oxide was utilized for the regeneration of the catalyst . Kam and Oppenheimer also pursued the dihydroxylation route for the synthesis of carbocyclic ribofuranosylamine and lyxofuranosylamine compounds .…”