Ligand-controlled palladium-catalyzed divergent synthesis of isonitriles and nitriles from benzylic carbonates and TMSCN has been developed. The BINAP- or DPEphos-ligated palladium catalyst selectively provides the corresponding benzylic isonitriles, whereas their regioisomers, benzylic nitriles, are formed exclusively under phosphine ligand-free conditions. Mechanistic studies reveal that isonitrile is the primary product under both conditions, but it is isomerized into nitrile in the absence of ancillary phosphine ligands.

中文翻译：

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钯催化苯甲酰胺与TMSCN取代合成异腈和腈

已经开发了由碳酸苄基酯和TMSCN进行配体控制的钯催化的异腈和腈的发散合成。BINAP或DPEphos连接的钯催化剂选择性地提供相应的苄基异腈，而它们的区域异构体苄基腈仅在无膦配体的条件下形成。机理研究表明，在两种条件下，异腈都是主要产物，但在没有辅助膦配体的情况下，它会异构化为腈。