钯催化的分子内卡宾插入 C(sp(3) )-H 键。
Palladium-Catalyzed Intramolecular Carbene Insertion into C(sp(3) )-H Bonds.
机构信息
Laboratori de Química Orgànica, Facultat de Farmàcia, Universitat de Barcelona, Av. Joan XXIII s/n, 08028, Barcelona, Spain.
Departamento de Química Orgánica I, Facultad de Ciencias Químicas, Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad Complutense de Madrid, Ciudad Universitaria, 28040, Madrid, Spain.
出版信息
Angew Chem Int Ed Engl. 2016 May 23;55(22):6467-70. doi: 10.1002/anie.201602020. Epub 2016 Apr 15.
A palladium-catalyzed carbene insertion into C(sp(3) )-H bonds leading to pyrrolidines was developed. The coupling reaction can be catalyzed by both Pd(0) and Pd(II) , is regioselective, and shows a broad functional group tolerance. This reaction is the first example of palladium-catalyzed C(sp(3) )-C(sp(3) ) bond assembly starting from diazocarbonyl compounds. DFT calculations revealed that this direct C(sp(3) )-H bond functionalization reaction involves an unprecedented concerted metalation-deprotonation step.
发展了钯催化的卡宾插入 C(sp(3) )-H 键生成吡咯烷的反应。该偶联反应可以被 Pd(0) 和 Pd(II) 催化，具有区域选择性，并且对各种官能团具有很好的耐受性。这是首例钯催化的由重氮化合物引发的 C(sp(3) )-C(sp(3) )键偶联反应。DFT 计算表明，这种直接的 C(sp(3) )-H 键官能团化反应涉及前所未有的协同金属化-脱质子步骤。
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