All at once arrangement of both oxygen atoms of dioxygen into aliphatic C(sp(3))-C(sp(3)) bonds for hydroxyketone difunctionalization
All at once arrangement of both oxygen atoms of dioxygen into aliphatic C(sp(3))-C(sp(3)) bonds for hydroxyketone difunctionalization
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双氧的两个氧原子同时排列成脂肪族 C(sp(3))-C(sp(3)) 键以进行羟基酮双官能化
DOI：
10.1007/s11426-020-9949-7
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Zhao Jincai
中科院分区：
文献类型：
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作者：
Qiao Xiaofeng;Lin Yuhan;Li Jiazhen;Ma Wanhong;Zhao Jincai
β-和γ-羟基酮结构是生物活性分子、合成药物和精细化学品的重要单元。虽然有一些途径可用于从一个或两个基质分子上的预官能化基团制备它们，但是简单地且同时地将两个氧原子从分子氧存款到纯饱和烃的两个特定C（sp3）位置的方法很少成功，因为它们涉及三个惰性C-H σ键的靶向活化。在这里，我们表明，TiO 2-CH 3CN光催化悬浮体系能够插入到一个C（sp3）-C（sp3）键的应变环烷烃衍生物，通过该双官能化的羟基酮产品在一锅反应中获得的二氧。以裂解释放应变为定向驱动力，设计的光催化反应体系中，三元环衍生物的β-羟基酮产物有21个，分离产率为31%~ 76%，四元环底物的γ-羟基酮产物有5个，分离产率为30%~ 63%。Ti 18 O2和有意添加的H218 O分别表明，羟基酮产物的两个氧原子完全来自分子氧，这表明氢过氧化物中间体将分子氧转化为羟基酮单元的先前未知的H+/TiO 2-e−催化排列途径。
Both β- and γ- hydroxyketone structures are important units in biologically active molecules, synthetic drugs and fine chemicals. Although there are some routes available for their manufacture from pre-functionalized groups on one or two matrix molecule(s), the approaches to simply and simultaneously deposit two oxygen atoms from dioxygen into two specific C(sp3) positions of pure saturated hydrocarbons have rarely succeeded because they are involved in the targeted activation of three inert C-H σ bonds all at once. Here, we show that a TiO2-CH3CN photocatalytic suspension system enables the insertion of dioxygen into one C(sp3)-C(sp3) bond of strained cycloparaffin derivatives, by which difunctionalized hydroxyketone products are obtained in a one-pot reaction. With the cleavage event to release strain as the directional driving force, as-designed photocatalytic reaction systems show 21 examples of β-hydroxyketone products with 31%–76% isolated yields for three-membered ring derivatives and 5 examples of γ-hydroxyketone products with 30%–63% isolated yields for four-membered ring substrates.18O isotopic labeling experiments using18O2, Ti18O2and intentionally added H218O, respectively, indicated that both oxygen atoms of hydroxyketone products were exclusively from dioxygen, suggesting a previously unknown H+/TiO2-e−catalyzed arrangement pathway of the hydroperoxide intermediate to convert dioxygen into hydroxyketone units.