Escape from Hydrofunctionalization: Palladium Hydride-Enabled Difunctionalization of Conjugated Dienes and Enynes.
Escape from Hydrofunctionalization: Palladium Hydride-Enabled Difunctionalization of Conjugated Dienes and Enynes.
复制标题
逃离氢官能化：氢化钯使共轭二烯和烯炔双官能化。
DOI：
10.1002/anie.202311848
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Gevorgyan,Vladimir
中科院分区：
文献类型：
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作者：
Zhang,Ziyan;Gevorgyan,Vladimir
氢化钯传统上用于共轭二烯和烯炔的氢官能化（即单官能化），因为它易于对富电子（或中性）不饱和键进行质子氢钯化。在此，我们报道了共轭二烯和烯炔的温和 PdH 催化双官能化。该协议是通过初始水钯化步骤的化学选择性开关来实现的，该开关是通过可见光增强 PdH 物质的水度来实现的。该方法允许二烯和烯炔与各种容易获得且丰富的底物（例如丙烯酸、丙烯酰胺和贝利斯-希尔曼加合物）进行级联环化，生成各种烯基或炔基内酯、内酰胺和四氢呋喃。该协议还提供了对复杂螺稠合三环框架的轻松访问。
Palladium hydrides are traditionally employed in hydrofunctionalization (i.e. monofunctionalization) of conjugated dienes and enynes, owning to its facile protic hydropalladation of electron‐rich (or neutral) unsaturated bonds. Herein, we report a mild PdH‐catalyzed difunctionalization of conjugated dienes and enynes. This protocol is enabled by the chemoselectivity switch of the initial hydropalladation step achieved by visible light enhancement of hydricity of PdH species. This method allows for cascade annulation of dienes and enynes with various easily available and abundant substrates, such as acrylic acids, acrylic amides, and Baylis–Hillman adducts, toward a wide range of alkenyl or alkynyl lactones, lactams, and tetrahydrofurans. This protocol also provides an easy access to complex spiro‐fused tricyclic frameworks.