Isonitriles as Stereoelectronic Chameleons: The Donor-Acceptor Dichotomy in Radical Additions

ChemRxiv
Gabriel dos Passos GomesIgor Alabugin

Abstract

This study started from a simple question of why isonitriles and alkynes (the two functional groups that look so much alike in their ground states) provide drastically different type of products in addition reactions. Whereas addition to alkynes proceeds in a “1,2-addition” where the new bonds are formed at the different alkyne carbons, isonitriles can react via “1,1-insertion” by forming both new bonds at the same terminal carbon of the isonitrile moiety. Such outcome is consistent with the hidden carbene nature of the isonitrile functionality. Due to the ability of serving as 1,1-synthons, isonitriles lend themselves to a variety of annulations where they serve as a one-carbon component in assembly of carbo- or heterocycles (e.g., [4+1] annulations pioneered by Curran) or, with a change of reactant topology, as two-atom components in the assembly of heterocycles. Our hypothesis was this behavior should be associated wtih additional state-crossings that corresponds to intramolecular charge and spin-transfer between nitrogen and carbon. Understanding of such dynamic state interconversion may unlock new electronic effects, not available to alkynes. From the practical perspective, such conceptual understanding can lead to the des...Continue Reading

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