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

• Published in: Journal of the American Chemical Society Vol. 140; no. 43; pp. 14272 - 14288
• Main Authors: Gomes, Gabriel dos Passos, Loginova, Yulia, Vatsadze, Sergey Z, Alabugin, Igor V
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 31.10.2018
• Subjects: carbon; chemical bonding; free radicals; thermodynamics; tin

Radical addition to isonitriles (isocyanides) starts and continues all the way to the transition state (TS) mostly as a simple addition to a polarized π-bond. Only after the TS has been passed, the spin density moves to the α-carbon to form the imidoyl radical, the hallmark intermediate of the 1,1-a...