Title of article :
Co(thd)2: a superior catalyst for aerobic epoxidation and hydroperoxysilylation of unactivated alkenes: application to the synthesis of spiro-1,2,4-trioxanes
Author/Authors :
OʹNeill، نويسنده , , Paul M. and Hindley، نويسنده , , Stephen and Pugh، نويسنده , , Matthew D. and Davies، نويسنده , , Jill and Bray، نويسنده , , Patrick G. and Park، نويسنده , , B.Kevin and Kapu، نويسنده , , Dauda S. and Ward، نويسنده , , Stephen A. and Stocks، نويسنده , , Paul A.، نويسنده ,
Abstract :
Bis(2,2,6,6-tetramethyl-3,5-heptanedionato)cobalt(II) (Co(thd)2), a β-diketonate prepared in a simple one-step procedure, is an excellent catalyst for aerobic epoxidation and Mukaiyama–Isayama hydroperoxysilylation of unactivated alkenes. For hydroperoxysilylation, Co(thd)2 is superior to Co(acac)2 and can catalyse oxidation of cyclic alkenes in excellent yield. Chiral β-diketonate or keto iminato catalysts failed to catalyse this reaction in an enantioselective manner and a free radical mechanism consistent with this observation is proposed. Hydroperoxysilylation of cyclohex-1-enylmethanol by Co(thd)2 followed by addition of a ketone/TsOH provides a simple one-pot procedure for the synthesis of spiro-1,2,4-trioxane antimalarials.
