废止
重氮
环加成
电泳剂
催化作用
化学
组合化学
三氟甲磺酸
基质(水族馆)
氢化物
药物化学
有机化学
金属
海洋学
地质学
作者
Ming Bao,Diana Victoria Navarrete Carriola,Daniel Wherritt,Michael P. Doyle
标识
DOI:10.1021/acscatal.4c01291
摘要
Highly selective formal [3 + 2]-cycloaddition of vinyldiazoacetates with quinone ketals and quinoneimine ketals has been accomplished at room temperature with catalytic amounts of the Brønsted acid triflimide, leading to highly functionalized diazoacetates in good yields. The vinyldiazonium ion generated by electrophilic addition to the vinylogous position of the reactant vinyldiazo compound is the key intermediate in this selective transformation. Both oximidovinyldiazoacetates and those with other vinyl substituents undergo cycloaddition reactions with quinone ketals whose products, after extended reaction times, undergo substrate-dependent 1,2-migration; catalysis by Rh2(OAc)4, HNTf2, and Sc(OTf)3 effects these 1,2-migrations to the same products. However, the products from HNTf2-catalyzed reactions between quinoneimine and oximidovinyldiazoacetates undergo Rh2(OAc)4-catalyzed 1,3-C–H insertion. 1,3-Difunctionalization products are obtained for electrophilic reactions of Eschenmoser's salt with selected vinyldiazoacetates, but with α-dibenzylaminomethyl ether, 1,6-hydride transfer reactions are observed with oximidovinyldiazoacetates.
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