Nickel‐Catalyzed Three‐Component Coupling Reactions of Iodobenzenes, an Isocyanide, and a Disilathiane: Access to Cyclic Thioimidates and Secondary Thioamides

We demonstrate that a Ni(II)/ t ‐BuOK catalytic system effectively catalyzes the three‐component coupling (TCC) reactions of 2‐ethynyliodobenzenes, t ‐butyl isocyanide, and hexamethyldisilathiane to produce various 3‐benzylidene‐ N ‐( t ‐butyl)benzo[ c ]thiophen‐1‐imine derivatives with a cyclic thioimidate skeleton. The disilathiane was successfully utilized as the sulfur source and can be embedded in a ring structure. Moreover, iodobenzene can undergo the same intermolecular TCC reactions, effectively affording secondary thioamide derivatives.