Aerobic Carbon–Carbon Bond Cleavage of Alkenes to Aldehydes Catalyzed by First-Row Transition-Metal-Substituted Polyoxometalates in the Presence of Nitrogen Dioxide,Journal of the American Chemical Society

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Aerobic Carbon–Carbon Bond Cleavage of Alkenes to Aldehydes Catalyzed by First-Row Transition-Metal-Substituted Polyoxometalates in the Presence of Nitrogen Dioxide
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2014-07-23 , DOI: 10.1021/ja502846h
Amir Rubinstein ₁ , Pablo Jiménez-Lozanao ₂ , Jorge J. Carbó ₂ , Josep M. Poblet ₂ , Ronny Neumann ₁

Affiliation

A new aerobic carbon-carbon bond cleavage reaction of linear di-substituted alkenes, to yield the corresponding aldehydes/ketones in high selectivity under mild reaction conditions, is described using copper(II)-substituted polyoxometalates, such as {α2-Cu(L)P2W17O61}(8-) or {[(Cu(L)]2WZn(ZnW9O34)2}(12-), as catalysts, where L = NO2. A biorenewable-based substrate, methyl oleate, gave methyl 8-formyloctanoate and nonanal in >90% yield. Interestingly, cylcoalkenes yield the corresponding epoxides as products. These catalysts either can be prepared by pretreatment of the aqua-coordinated polyoxometalates (L = H2O) with NO2 or are formed in situ when the reactions are carried with nitroalkanes (for example, nitroethane) as solvents or cosolvents. Nitroethane was shown to release NO2 under reaction conditions. (31)P NMR shows that the Cu-NO2-substituted polyoxometalates act as oxygen donors to the C-C double bond, yielding a Cu-NO product that is reoxidized to Cu-NO2 under reaction conditions to complete a catalytic cycle. Stoichiometric reactions and kinetic measurements using {α2-Co(NO2)P2W17O61}(8-) as oxidant and trans-stilbene derivatives as substrates point toward a reaction mechanism for C-C bond cleavage involving two molecules of {α2-Co(NO2)P2W17O61}(8-) and one molecule of trans-stilbene that is sufficiently stable at room temperature to be observed by (31)P NMR.

中文翻译：

在二氧化氮存在下，第一排过渡金属取代的多金属氧酸盐催化烯烃的碳-碳键有氧裂解为醛

(31)P NMR 表明，Cu-NO2 取代的多金属氧酸盐充当 CC 双键的氧供体，产生 Cu-NO 产物，该产物在反应条件下重新氧化为 Cu-NO2 以完成催化循环。使用 {α2-Co(NO2)P2W17O61}(8-) 作为氧化剂和反式二苯乙烯衍生物作为底物的化学计量反应和动力学测量表明 CC 键断裂的反应机制涉及两个 {α2-Co(NO2)P2W17O61} 分子(8-) 和一分子在室温下足够稳定的反式二苯乙烯，可以通过 (31)P NMR 观察到。

更新日期：2014-07-23

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