Palladium-Catalyzed Regiodivergent Three-Component Alkenylamination of 1,3-Dienes with Alkyl and Aryl Amines.
Palladium-Catalyzed Regiodivergent Three-Component Alkenylamination of 1,3-Dienes with Alkyl and Aryl Amines.
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DOI：
10.1021/jacs.3c09873
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发表时间：
2023-12
影响因子：
15
通讯作者：
Xiaoxiao Ma;Steven J. Malcolmson
中科院分区：
文献类型：
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作者：
Xiaoxiao Ma;Steven J. Malcolmson
我们报道了一种钯催化的4,3-或4,1-末端二烯选择性烯基层合的方法。三烯酸酯和几种胺进行三组分偶联，用xantphos负载的催化剂进行近端碳胺化，远端用酰胺磷配体进行二官能化。一些结构上不同的二取代二烯也参与了区域分散的碳胺化。实验表明，Xantphos反应的选择性很大程度上受底物的影响，而磷酸酰胺促进的反应过程是由催化剂控制的，由配体、溶剂和底物之间的关键π堆积相互作用精心安排。
We report a palladium-catalyzed method for 4,3- or 4,1-selective alkenylamination of terminal dienes. Three-component couplings proceed with alkenyl triflates and several amines, giving vicinal carboamination with a Xantphos-supported catalyst and distal difunctionalization with a phosphoramidite ligand. A number of constitutionally different disubstituted dienes also participate in regiodivergent carboaminations. Experimental evidence indicates that selectivity in the Xantphos reactions is largely influenced by the substrate, whereas the phosphoramidite-promoted process is catalyst controlled, orchestrated by a key π-stacking interaction among the ligand, solvent, and substrate.