1801-76-9Relevant articles and documents
Stereoselective oxidation of linalool with tert-butyl hydroperoxide, catalyzed by a vanadium(V) complex with a chiral terpenoid ligand
Bryliakov,Talsi,Stas'ko,Kholdeeva,Popov,Tkachev
, p. 79 - 88 (2003)
Stereoselective epoxidation of (-)-(R)-linalool by tert-butylhydroperoxide (TBHP) catalyzed by a V complex formed by interaction of [VO(acac)2] or [VO(On-Bu)3] with a new chiral terpenoid ligand was presented. The oxidation of (-)-(R)-linalool with TBHP in the presence of [VO(acac)2] in toluene led to the formation of two diastereomeric monoepoxides, (2S,3R) and (2R,3R), with a poor diastereomeric excess (de 4%, Run 1). The use of CH2Cl2 and CCl4 instead of toluene resulted in the de decrease, while in the presence of MeCN as a solvent, the reaction did not proceed. The oxidation of racemic linalool revealed that a kinetic resolution of the allylic alcohol takes place: at 70% conversion the yield of the (2R,3S)+( 2S,3S) diastromers was 5-fold higher than the yield of the (2S, 2R) + (2R, 3R) diastereomeric pair. Thus, (+)-(S)-linalool oxidation rate was higher as compared to (-)-(R)-linalool. The 51V chemical shift of complex 1 in CH2Cl2 was affected by the presence of TBHP, indicating fast exchange between at least two forms existing in solution. When the concentration of TBHP increased, the 51V signal shifted upfield monotonically.
