Rh-Catalyzed Intermolecular Reactions of α-Alkyl-α-Diazo Carbonyl Compounds with Selectivity over β-Hydride Migration.
Rh-Catalyzed Intermolecular Reactions of α-Alkyl-α-Diazo Carbonyl Compounds with Selectivity over β-Hydride Migration.
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DOI：
10.1021/acs.accounts.5b00425
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发表时间：
2016-01-19
影响因子：
18.3
通讯作者：
Fox JM
中科院分区：
文献类型：
--
作者：
DeAngelis A;Panish R;Fox JM
衍生自α-重氮羰基化合物的Rh-卡宾已发现在显著范围的反应性中具有广泛的用途，包括环丙烷化、环丙烯化、C-H插入、杂原子-H插入和叶立德形成反应。然而，与α-芳基或α-乙烯基-α-重氮羰基化合物相反，α-烷基-α-重氮羰基化合物的用途由于此类化合物进行分子内β-氢化物迁移以产生烯烃产物的倾向而受到限制。特别具有挑战性的是涉及α-烷基-α-重氮羰基化合物的分子间反应。
Rh-carbenes derived from α-diazocarbonyl compounds have found broad utility across a remarkable range of reactivity, including cyclopropanation, cyclopropenation, C–H insertions, heteroatom–H insertions, and ylide forming reactions. However, in contrast to α-aryl or α-vinyl-α-diazocarbonyl compounds, the utility of α-alkyl-α-diazocarbonyl compounds had been moderated by the propensity of such compounds to undergo intramolecular β-hydride migration to give alkene products. Especially challenging had been intermolecular reactions involving α-alkyl-α-diazocarbonyl compounds.