铜催化芳基重氮乙酸酯与双[(频哪醇)硼基]甲烷的偶联反应  

Copper-Catalyzed Cross-Coupling of Aryldiazoacetates with Bis[(pinacolato)boryl]methane

作　　者：鲍志成 李慕尧 王剑波[1] Bao Zhicheng;Li Muyao;Wang Jianbo(Beijing National Laboratory of Molecular Sciences,College of Chemistry and Molecular Engineering,Peking University,Beijing 100871)

机构地区：[1]北京大学化学与分子工程学院,北京分子科学国家研究中心,北京100871

出　　处：《有机化学》2023年第5期1808-1814,共7页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.21871010)资助项目。

摘　　要：报道铜催化下重氮苯乙酸酯作为卡宾前体与双[(频哪醇)硼基]甲烷的交叉偶联反应,实现sp^(3)-杂化碳碳键的构筑.条件筛选表明亚磷酰胺配体monophos对该反应的成功尤为关键.原位氧化使得硼酯产物以醇的形式被分离,反应具有高效率以及良好的官能团兼容性.该两步反应是芳基重氮酯类化合物形式上的羟甲基化.The copper-catalyzed cross-coupling reaction of 1,1-bis[(pinacolato)boryl]methane with α-diazophenylacetate as carbene precursor was reported,leading to the construction of C(sp^(3))—C(sp^(3)) bond.Reaction optimization experiments showed that Monophos ligand was critical for the success of this reaction.In situ oxidation afforded the corresponding primary alcohols instead of the relatively unstable boronates.The reaction has high efficiency and good functional group compatibility.The two-step transformation represents a formal hydroxymethylation of diazoacetates.

关 键 词：铜催化 sp^(3)-杂化碳碳键构筑 重氮化合物 双[(频哪醇)硼基]甲烷 

分 类 号：O621.251[理学—有机化学]