cis-2,6-Bis-(methanolate)-piperidine oxovanadium(V) complexes as catalysts for oxidative alkenol cyclization by tert-butyl hydroperoxide

Abstract cis -2,6-Bis-(methanolate)-piperidine oxovanadium(V) complexes are Lewis acids able to catalyze oxidative cyclization of alkenols by tert -butyl hydroperoxide (TBHP). Terminal dimethyl-substituted (prenyl-type) 4-pentenols bearing an alkyl or a phenyl group in position 1 afford under such conditions 2,5- cis -derivatives of 2-(tetrahydrofuran-2-yl)-2-propanol as major and tetrahydropyran-3-ols as minor products (four examples). Oxidizing 1-phenyl-6-methylhept-5-en-1-ol yields a 75/25-mixture of the derived 2-(tetrahydropyran-2-yl)-2-propanol and an oxepan-3-ol, whereas 2-propenols give epoxides in up to 94% yield. Epoxidizing geraniol by TBHP in the presence of a vanadium catalyst prepared from (2 S ,6 R )-2-diphenylmethanol-6-hydroxymethylpiperidine occurs enantioselectively. Highfield shifts of vanadium-51 resonances upon adding alkyl hydroperoxides to solutions of cis -2,6-bis-(methanolate)-piperidine vanadium(V) complexes point to vanadium(V) tert -butyl peroxy complex formation as key step for activating peroxides.