通过支链选择性钯催化烯丙基烷基化反应在对映体富集的重氮化合物中形成邻位二级和全碳季碳立体中心。
Formation of Vicinal Secondary and All-Carbon Quaternary Stereocenters in Enantioenriched Diazenes via Branched-Selective Pd-Catalyzed Allylic Alkylation.
作者信息
Zoll Adam J, Cerione Chloe S, Virgil Scott C, Stoltz Brian M
机构信息
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
出版信息
Tetrahedron Lett. 2025 Jul 30;165-166. doi: 10.1016/j.tetlet.2025.155657. Epub 2025 May 16.
Abstract
The synthesis of enantioenriched alkyl diazenes with vicinal secondary and all carbon quaternary stereocenters via palladium-catalyzed allylic alkylation is reported. Diazenes were formed in high diastereoselectivity and modest enantioselectivity. Notably, the ratio of branched to linear products was very high, a rarely observed phenomenon in palladium catalysis. The utility of this approach was demonstrated by cleaving the N=N bond to form an α-secondary amine with a vicinal all-carbon quaternary stereocenter.
摘要
报道了通过钯催化的烯丙基烷基化反应合成具有邻位仲碳和全碳季碳立体中心的对映体富集烷基重氮化合物。重氮化合物以高非对映选择性和适度的对映选择性形成。值得注意的是，支链产物与线性产物的比例非常高，这在钯催化中是很少观察到的现象。通过裂解N=N键形成具有邻位全碳季碳立体中心的α-仲胺，证明了该方法的实用性。
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