Oxidative functional group transformations with hydrogen peroxide catalyzed by a divanadium-substituted phosphotungstate
作者:Noritaka Mizuno、Keigo Kamata、Kazuya Yamaguchi
DOI:10.1016/j.cattod.2011.07.007
日期:2012.5
equivalent H+ to form a bis-μ-hydroxo species [γ-PW10O38V2(μ-OH)2]3− (I′) in organic media. The strong electrophilic oxidants such as [γ-PW10O38V2(μ-OH)(μ-OOH)]3− (II) and [γ-PW10O38V2(μ-η2:η2-O2)]3− (III) are formed by the reaction of the bis-μ-hydroxo species with H2O2. In the presence of I and H+, H2O2-based oxidations such as (i) epoxidation of alkenes (17 examples including electron-deficient ones),
甲二钒取代的磷钨TBA 4 [γ-PW 10 ö 38 V 2(μ-OH)(μ-O)](我,TBA =四Ñ -butylammonium)与一种当量H起反应+以形成双- μ -hydroxo物种[γ-PW 10 ö 38 V 2(μ-OH)2 ] 3-(我')在有机介质中。强电氧化剂如[γ-PW 10 ö 38 V 2(μ-OH)(μ-OOH)] 3-(II)和[γ-PW 10 ö 38 V 2(μ-η 2:η 2 -O 2)] 3-(III)是通过用H双- μ-羟物种的反应形成2 Ò 2。在I和H +的存在下,基于H 2 O 2的氧化,例如(i)烯烃的环氧化(17个实例,包括缺电子的烯烃),(ii)烷烃的羟基化(11个实例),以及(iii)氧化烯烃,炔烃,并与溴芳烃的溴化-作为溴源(包括氯化的12个例子),化学,非对映体和区域选择性地以中等至高收率,高效率地利用H 2 O 2来产生相应的氧化产物。